The Espada were created through various means, though one unique case is that of Tia Harribel and her Fraccion: unlike the other Arrancar under Aizen's command, they were brainwashed into serving him, even though their true allegiance was to Ben Tennyson.
When Ben Tennyson arrived at Las Noches, the Espada were all quite surprised by his shape-shifting abilities. Aizen manipulated Ben into joining him, and Ben eventually became one of Harribel's Fraccion - she and her other Fraccion did not remember him, and their previous meeting had yet to occur in his timeline. Over time, Ben developed a rivalry with some of the Espada, most notably Nnoitra Jiruga and Baraggan Luisenbarn. In contrast, Harribel fell in love with him.
At one point, Ben was offered the position of Sexta (Sixth) Espada when Grimmjow Jaegerjaquez was demoted, but he declined the position, which ultimately went to Luppi Antenor. Luppi was eventually killed by Grimmjow after the latter regained his powers thanks to Orihime Inoue, allowing Grimmjow to regain his status as the Sexta Espada.
Invasion of Las NochesEdit
Eventually, Ben learned the truth of Aizen's plans and defected, along with Harribel, her Fraccion, and a recently restored Nelliel Tu Odeschwanck. This coincided with an attack on Las Noches]] mounted by Ichigo Kurosaki and his friends, and later several Gotei 13 captains. Aaroniero Arruruerie and Zommari Leroux were some of the first casualties, being slain by Rukia Kuchiki and her brother-in-law/adoptive brother Byakuya Kuchiki, respectively.
Nnoitra and Szayel Aporro Granz were defeated by Ben, but later teamed up and attacked him and his friends. The fight was interrupted by Kenpachi Zaraki and Mayuri Kurotsuchi, who took over the fight and killed Nnoitra and Szayel, respectively. In the meantime, Ichigo defeated Grimmjow but left him alive. Later, Ulquiorra Cifer was defeated by Hollow Ichigo, but was healed by Professor Paradox who subsequently convinced him to step aside and not hinder the heroes.
Fake Karakura TownEdit
Arriving at Fake Karakura Town with his friends, Ben convinced Coyote Starrk and Lilynette Gingerbuck to betray Aizen. The two then killed Baraggan Luisenbarn, who held a deep grudge against Ben and thus would not defect, despite his equally intense hatred for Aizen himself: Aizen was amused by the irony that the "one Espada who did not betray [him] was the one who hated [him] the most." The defectors were fatally wounded by Aizen in the subsequent battle but were healed by Alien X, Ben's most powerful form, after he defeated Aizen.
Following Aizen's defeat, Grimmjow - having been healed by Retsu Unohana - became the king of Hueco Mundo, while the others chose to stay in the human world, despite protests from some of the Gotei 13. Harribel, her Fraccion, and Nelliel moved to Ben's house in Bellwood; Starrk and Lilynette moved in with Gwen Tennyson, Ben's cousin; Ulquiorra relocated to Los Soledad; and the various surviving Fraccion (minus Loly Aivirrne and Menoly Mallia moved to various places, though most of them set up base somewhere in Bellwood.
They also took up various occupations: Harribel became a Spanish teacher at the Ben's high school; her Fraccion were enrolled as students in the same school; Starrk became a bounty hunter; Lilynette was enrolled in elementary school (much to her annoyance); Nelliel got a job at a book store; and Ulquiorra became a private detective. The other Arrancar, depending on their physical appearances, either had to enroll in school or get jobs, as well.
|0||Yammy Llargo (Post-Release)||Deceased: Killed by Byakuya Kuchiki & Kenpachi Zaraki|
|1st||Coyote Starrk & Lilynette Gingerbuck (Post-Release)||Alive: Defected to Ben Tennyson|
|2nd||Baraggan Luisenbarn||Deceased: Killed by Coyote Starrk & Lilynette Gingerbuck|
|3rd||Nelliel Tu Odelschwanck||Alive: Defected to Ben Tennyson|
|3rd||Tia Harribel||Alive: Defected to Ben Tennyson|
|4th||Ulquiorra Cifer||Alive: Defeated by Hollow Ichigo, later healed by Professor Paradox and joined Ben Tennyson|
|5th||Nnoitra Jiruga||Deceased: Killed by Kenpachi Zaraki|
|6th||Luppi Antenor||Deceased: Killed by Grimmjow Jaegerjaquez|
|6th||Grimmjow Jaegerjaquez||Alive: Defeated by Ichigo Kurosaki, later healed by Retsu Unohana|
|7th||Zommari Leroux||Deceased: Killed by Byakuya Kuchiki|
|8th||Szayel Aporro Granz||Deceased: Killed by Mayuri Kurotsuchi|
|9th||Aaroniero Arruruerie||Deceased: Killed by Rukia Kuchiki|
|103rd||Dordoni Alessandro Del Socaccio||Deceased: Defeated by Ichigo Kurosaki, killed by Rudobon Chelute|
|105th||Cirucci Sanderwicci||Deceased: Defeated by Uryu Ishida, killed by Rudobon Chelute|
|107th||Gantenbainne Mosqueda||Alive: Defected to Ben Tennyson|