Attacking the Human WorldLuppi was promoted to position of 6th Espada after Grimmjow Jaegerjaquez had his arm cut off and burned away by Kaname Tōsen. He attended Wonderweiss Margela's transformation into a Arrancar and went with Yammy Llargo, Wonderweiss, and Grimmjow to attack the human world. They arrived via Garganta and after Grimmjow leapt off to find Ichigo Kurosaki, Luppi and the others engaged Toshiro Hitsugaya, Rangiku Matsumoto, Ikkaku Madarame, and Yumichika Ayasegawa. After easily swatting away Yumichika, Luppi told Yammy that he wanted to fight all of them at once and began to release his Zanpakuto. He succeeded, despite Toshiro's attempts to stop him, and struck at the captain with one of his tentacles out of the smoke cloud generated by the release. Toshiro managed to block it and Luppi complimented him for having the strength to do so, but as the smoke cleared, he asked if he could have blocked it if it was eight times stronger. The 6th Espada then lashed out at Toshiro with all his tentacles and the blow sent him falling to the ground. Luppi turned his attention to the other Shinigami and said they should have fought him four on 1. He engaged Rangiku, Ikkaku, and Yumichika and easily beat them before subduing them with his tentacles. Luppi prepared to finish Rangiku off, but Kisuke Urahara showed up and sliced off the ends of some of his tentacles that were holding the lieutenant. The 6th Espada asked him who he was and after Kisuke introduced himself, Wonderweiss attacked him, allowing Luppi to return his attention to the other Shinigami. He easily subdued Rangiku again and scorned her for being recaptured so easily, only for the lieutenant to say he talked too much, which she found disgusting. Luppi angrily threatened to skewer her, before Toshiro froze all his tentacles and criticized him for not making sure to finish him off. The captain proceeded to encase the 6th Espada in ice using his Bankai, but a Negación shattered the ice, freeing Luppi. The 6th Espada headed for a Garganta back to Las Noches, but swore to kill Toshiro next time they met.
DeathUpon returning to Las Noches, Luppi expressed outrage at the fact that the attack was only a means of capturing Orihime Inoue. Aizen asked Orihime to demonstrate her powers by healing Grimmjow's missing arm, but Luppi said that that was impossible since she couldn't heal something that no longer existed. Orihime started to use her powers and the 6th Espada said that she was just trying to prove her worth to Aizen, calling her power fake and threatening to kill her when she didn't succeed. But when she succeeded, Luppi was shocked and Aizen explained that her powers were beyond just healing. Grimmjow asked Orihime to heal the scar where his Espada tattoo used to be and Luppi demanded to know what he was doing. However Grimmjow proceeded to impale him and Luppi used his last breath to curse him, before Grimmjow taunted him and blew away the top half of his body with a Cero.
The most prominent part of Luppi Antenor's personality is his extreme arrogance, boasting frequently in battle, and he enjoys constantly taunting Grimmjow for losing his Espada rank. He often mocks people by sarcastically apologizing after insulting them and has a habit of licking his lips in battle. Luppi seems to be quite friendly towards Gin Ichimaru, since Gin said he felt lonely after his death, so the two apparently spoke to each other. In battle, he finds no enjoyment in fighting opponents that don't pose a challenge and often asks multiple foes to fight him at once. Luppi enjoys toying with people he fights, especially if he doesn't think they're a threat, though even the slightest taunts greatly irritate him. He is easily one to hold a grudge as seen when he swore to twist off Toshiro's head when they next met after surviving his attack. Luppi is also apparently somewhat perverted since he commented on Rangiku's body when he had her subdued.
PowersLuppi possesses great spiritual power, reflected in his position as one of the Espada, and proved able to easily take on a Shinigami captain, lieutenant, and two lieutenant level Shinigami in battle. Like all Arrancar, he is able to enter Resurrección by releasing his Zanpakuto, Trepadora, with the release command "Strangle". When he does so, he gains an increase in power and a set of eight tentacles form on Luppi's back in an octagon shape that he can use to attack his enemies and they can sprout spikes on the end to impale his opponents.
- In Luppi's first manga appearance, the Hollow Mask remnant on his head had more teeth than it did throughout the rest of the series.
- In his Resurrección form, his tentacles are attached to his back in a shape similar to the Chinese symbol Ba Gua.
- The name of Luppi's Zanpakuto is "Climbing Vine" in Spanish and "Ivy Girl" in Japanese.