In What episode does Ulquiorra and ichigo fight for the second time?

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Ulquiorra and Ichigo fight for the second time in the Anime Bleach Episode 266 (Season 14) with the title “Ichigo vs. Ulquiorra,” ( or “護VSウルキオラ、再開!” in original japanese kanji) . 

 

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Episode Summary:

Aizen, Tosen, Gin, and the Espadas arrive at the fake Karakura Town, where they engage the Soul Society in battle. Meanwhile elsewhere Ichigo after defeating his opponent, quickly heads to the tower in which Inoue Orihime was being held. Bursting through the floor Ichigo finds both Ulquiorra and Inoue together, a bit relieved to see that she was alright, Ichigo then asks Ulquiorra to let her go which he accepts consenting that he was not given any orders to kill her but to protect Los Noches until Aizen returned; But killing Ichigo and protecting Los Noches go hand in hand. Near the conclusion of the episode Ulquiorra immediately drew his sword to show that he was serious about killing. Then both him and Ichigo hurl themselves at each other with swords clashing.

Aizen Tosen Gin-and Espadas Ichigo Arrives Castle
Ulquiorra draws sword Sword Clash