After a recap of Ichigo's battles with Ulquiorra and Grimmjow, Ichigo takes Orihime and Nel and prepares to leave but an injured Grimmjow refuses to accept defeat. Ichigo tells him that it is over but their conversation is interrupted by the intervention of an unexpected enemy. Meanwhile, Uryuu and Renji find themselves in another bad situation.

Renji and Uryuu find themselves back in the same room as before with Szayel Aporro waiting for them. He transforms and attacks with strange techniques that catch the group by surprise. Meanwhile, Ichigo struggles to hold his own against the 5th Espada Noitora. The injuries from his previous battle weigh him down but his opponent is relentless. Noitora reveals a startling secret about Nel's past.

The fight between Nnoitra and Ichigo gets more desperate as Nnoitra is about to crush Nel's head. Ichigo saves her, but Nnoitra brutally throws Ichigo out of the way each time he attempts to stop him. Nnoitra's moves get more aggressive until he begins to break Ichigo's arm. The intensity of Nel's emotions unleash an unintentional transformation to her original adult form. Nel then reveals that she has the rank of the former 3rd Espada- Neliel tu Oderschvank-, and begins to overpower Nnoitra. Nnoitra, however, is not easily defeated, even surviving Nel's powerful Cero Doble technique, and reveals that while Neliel once outranked him, the Espada have grown more powerful in her absence.

Uryu and Renji struggle against their clones. Szayel reveals a second ability: he is able to create voodoo dolls of an opponent by wrapping them in his wings. He succeeds with Uryu and Renji, and shows that by using them, he can cause pain to the targets and damage their internal organs. Meanwhile, Nnoitra is still losing to Neliel, but they hesitate before they can deal each other fatal blows, and Nnoitra notes that he has despised Neliel even before her departure.

Neliel's past is revealed through her fight with Nnoitra. Meanwhile, Pesche and Dondochakka mounts an offensive against Szayel after seeing Renji struggling against the Espada. Pesche thinks back to the time when Nnoitra attacked Neliel for power which ultimately ended with breaking Neliel's mask through the guidance of Szayel. She is dumped by Nnoitra, along with Pesche and Dondochakka back out of Aizen's palace. Neliel obtains amnesia as her broken mask renders her into a child. To the present, Nnoitra taunts Neliel in regards to their past. Neliel then releases her Zanpakuto, shouting "Declare...!".

Neliel finishes calling out her sword, Gamuza, and transforms into a white centaur. Before finishing her opponent, she suddenly transforms back to her child form. Meanwhile, Pesche Guatiche and Dondochakka Bilstin fight Szayel, using their Bawabawa. Pesche takes out his sword, Ultima, as he lands a strike on Szayel. As the fights go on, Dondochakka takes out his club to help out. Pesche and Dondochakka use their ultimate attack, "cero sincrecito", a combination of Dondochakka and Pesche's cero. Szyael manages to render their attack ineffective, and prepares to finish them off. Meanwhile, the Exequias prepare to kill Gantenbaine and Chad, and Zommari prepares to kill Rukia. Nnoitra sends Tesla to finish off Ichigo, and he releases his zanpakuto, turning into a large minotaur. Before Tesla can do so, 11th Divison Captain Kenpachi Zaraki stops him.

Kenpachi kills Tesla in one blow and tells Ichigo to stay out of his fight. He informs Ichigo that Urahara was tasked with making the Garganta into Hueco Mundo stable enough for the captains to enter, and that three others came with him. Retsu Unohana arrives with Isane Kotetsu, and persuades the Exequias to leave before healing Gantenbaine and Chad. Mayuri Kurotsuchi arrives and, despite Szayel creating a doll replica of him, remains confident that he can win. Byakuya arrives to save Rukia, and while Zommari nearly kills him with Gemelos Sonido, he manages to save himself with a technique that Yoruichi taught him.

Zommari, upset over Byakuya refusing to consider him an equal opponent, releases his zanpakuto, Brujeria, causing him to grow eyes all over his body that can control anything. He attempts to hinder Byakuya by controlling his left leg and arm, but Byakuya, realizing what is going on, severs the tendons and renders them useless. Hanatarou arrives and tries to get Rukia to safety, but Zommari uses his ability to control Rukia, who severely wounds Hanatarou, and demands that Byakuya surrender under the threat of making Rukia kill herself. Byakuya immobilizes Rukia with kido, and uses his bankai to attack Zommari, who is unable to control the countless blades to save himself.

Zommari survives Byakuya’s attack but Byakuya, having already discovered how to counter his ability to control others, quickly dispatches him. Mayuri initially seems unable to fight back against Szayel destroying his organs, but reveals that he has made himself immune to Szayel’s ability by replacing all the organs in his body after learning about the ability from bacteria he implanted in Uryu. He then activates his bankai, poisoning Szayel despite his efforts to make an antidote, then has it swallow Szayel.

Rukia regains consciousness, but is told to rest and regain her strength for the battles ahead. Kenpachi's battle with Nnoitra continues, and Orihime heals Nel at Ichigo's request. Despite managing to have his bankai swallow Szyael, Mayuri inadvertently poisons Uryu and Renji, and Szyael seizes the opportunity to resurrect himself by absorbing Nemu's spiritual particles through his Gabriel technique. However, in the process, he ingests a “super-human” drug from inside Nemu that increases his reflexes to the point where his body cannot keep up, immobilizing him. Mayuri then stabs him through the hand before stabbing him in the heart.

Szayel, his senses heightened as a result of the drug, feels Mayuri's zanpakuto piercing through his hand and heart for what seems like countless lifetimes before he dies. After restoring Nemu to full health, Mayuri orders her to clear away the rubble that concealed Szayel's laboratory. Afterwards, Mayuri heals the reluctant Uryu's injuries. Elsewhere, Kenpachi has difficulty cutting through Nnoitra's hierro, but believes that Nnoitra can be injured. Kenpachi manages to stab Nnoitra through his eyepatch, but Nnoitra counter-attacks, injuring Kenpachi, and reveals that he had stabbed him through his hollow hole. Kenpachi, unfazed, merely grins.

Kenpachi manages to wound Nnoitra with the slash, and finds the right amount of force he needs to put into his blows in order to cut his opponent. He continues to attack Nnoitra, and after Nnoitra accidentally tears off his eyepatch while trying to attack him, the limits on his power are removed, and he delivers a devastating slash to Nnoitra. Nnoitra then releases his zanpakuto, Santa Teresa, giving him an extra pair of arms and regenerative abilities. Nnoitra attacks Kenpachi and severely wounds him, but Kenpachi manages to cut off the arm. Nnoitra regenerates the arm and continues on the assault, growing yet another pair of arms and stabbing Kenpachi with one of his new arms.

Kenpachi continues fighting Nnoitra, and although he is able to keep up with his attacks, he realizes that he is in danger of dying. He then resorts to using kendo, and severely injures Nnoitra with a two-handed strike. Kenpachi attempts to leave, but Nnoitra insists that he finish their battle. Nnoitra recalls his time with Neliel, in which Neliel would frequently save him from his attempts to die in battle, and claims that he is angered by any display of pity from his opponent. He charges Kenpachi, who kills him.

After Kenpachi defeats Nnoitra, he demands Orihime heal him. Before Orihime reaches him, the Espada Stark arrives and takes her away to a tower where Sōsuke Aizen greets her. He informs her that he, Gin Ichimaru, and Kaname Tōsen are preparing to destroy Karakura Town. Aizen orders Tōsen to contact all of the Soul Reaper captains, Ichigo, and his friends with kidō, and reveals that he brought Orihime to Hueco Mundo to lure and trap them. As he travels through a garganta portal to Karakura Town, however, Aizen is confronted by Commander-General Shigekuni Yamamoto-Genryūsai, the leader of the Gotei 13, with five other captains. Aizen summons the Espada Stark, Barragan, and Halibel and orders Espada Ulquiorra Schiffer to protect Las Noches.

Back in the real world, Ichigo is in school when he happens upon Lurichiyo from the Kasumioji clan again, who it turns out has come back to the real world because she is angered that Kenryuu, her retainer, would not allow her to play soccer when she has other important duties to attend to. This leads to an outburst between Lurichiyo and Kenryuu, and the latter intends to end his life to make Lurichiyo "happy." After some persuasion from Ichigo and his friends, they manage to put on an act to fool Lurichiyo into forgiving him, but she ends up seeing through it. This leads to another argument about soccer and culminates in Lurichiyo challenging Kenryuu to a soccer game to see who is right once and for all.

The soccer game officially kicks off, with the referees being the proprietors from the Urahara Shop, Jinta and Ururu, with Urahara himself overseeing the proceedings, including setting up a gigantic barrier around the play field to designate the assigned area, which apparently is not legal in Soul Society's eyes. The two teams, each with varying characters, ranging from gigais to Kon, the modsoul, attempt to keep the ball away from each other using different and comical means. The action culminates in Ikkaku Madarame joining in the game, while actually sparring with Ichigo instead, under the impression that the latter was doing some intensive training, and a hollow which appears on the field, drawn by everyone's spiritual pressure. With the help of Ichigo, Chad and Uryu, the hollow is quickly dispatched and the game is over because the ball was dropped by Lurichiyo's team. Before she can lament about going back to her world, Shuu from the Kasumioji clan enters the human world via a Sen