Tōshirō Hitsugaya vs. Tier Harribel

Battle
While being surrounded Matsumoto offers her captain to take on all three Fracción, so that Hitsugaya can fight Harribel alone and undisturbed. After Hinamori arrived, Hitsugaya has flashback of when she asked him to help Aizen while Harribel asked why his Reiatsu became disordered. He answered her that he doesn’t know even though he was wondering why Hinamori was here.

Hitsugaya's match against Harribel seemed to have taken a new turn when the latter sensed her Fraccions' defeat. Harribel forces Hitsugaya back with sheer power from her blade swing and unzips her jacket, revealing her rank as the #3 Espada which is tattooed on her right breast. Hitsugaya is shocked to find out that Harribel is only #3 despite her strength. When Harribel taunts Hitsugaya that she has yet to fully demonstrate her strength, Hitsugaya quickly uses Bankai in an attempt to match her very sudden and large increase in power. Harribel rushes him and begins her attack as they come together and lock blades.

During this encounter Harribel knocks Tōshirō to the ground as she mocks him, questioning "whether this is the full strength of a captain". She then promises to end the battle and proceeds to release her Zanpakutō. After releasing, Tōshirō comments to himself that her appearance change hasn't changed as much as he predicted, but underestimating her would be a fatal mistake. However, Harribel proves to be in a different league then the young captain slicing the right side of his body from his shoulder before he even realizes it. Believing that Hitsugaya has been defeated, Harribel turns her attention to General Yamamoto, though before she can take any action toward him, she is attacked by an unseen assailant. Harribel dodges out of the way only to see that it is an unharmed Hitsugaya, she just as quickly countered his attacks. Noticeably confused as she had seen him cut down, she turns and sees that she has only struck down a ice clone. Hitsugaya claims that it was a one time technique that he was waiting to use for later in the battle but Harribel's considerable increase in power and speed as of her release was unexpected. He then comments to her not to underestimate a captain's strength.

As their fight ensues, he tells her that he can use any water around him, telling Harribel that she will never reach him. Hitsugaya then attacks Harribel. She reciprocates the situation by melting his ice and stating the iron law of battle. She finally attacks him with his melted ice. Their exchange of attacks continues and Hitsugaya tells her another law of battle. To which Harribel releases a Cero blast at him, which Hitsugaya comments on it being weak. He concludes that the reason her Cero was so weak, as both of them are waiting for the battlefield to become filled with condensation, from this he states that when that happens Harribel will use the opportunity to finish him off with one blow. Hitsugaya grows tired of waiting and states that he has never tried a particular ability in Bankai mode before, to which Harribel asks what he is talking about. Hitsugaya then explains that he doesn't have to wait for water, as Hyōrinmaru is the most powerful ice-based Zanpakutō, and all water is his weapon and all heaven is under his command.

He then reveals his never before seen power: Hyōten Hyakkasō. Hitsugaya then asks her name, to which she replies; Tia Harribel. Hitsugaya then states his name and rank before attacking again. As the sky darkens,snow begins to fall from the sky. Harribel attempts to melt the snow with her Hirviendo ability, but the moment her sword touches the snow, ice flowers begin to bloom on her body. Hitsugaya then calmly states that once all one hundred flowers have bloomed, she will die. He then states that she won't be able to avenge her underlings after all.

Aftermath
Seeing the huge creature emerge from the Garganta with Wonderweiss, Hitsugaya looks on at the events taking place. Wonderweiss lets out a huge wail that cracks the ice pillar Harribel is trapped in. Hitsugaya looks surprised as the ice pillar begins to fall apart from around her, and once free, she gazes at him.