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Tia Harribel (ティア・ハリベル, Tia Hariberu), pronounced Tia Hallibel in the English dub, is an Arrancar in Sōsuke Aizen's army, and is Espada Tres (Three). She is currently the only female Espada.

Harribel rarely speaks, and when she does, she's fairly serious. An example would be when she tells her Fracción that being afraid of an Espada's released form is a natural reaction. She calculated the battle between Ichigo Kurosaki and Grimmjow Jaegerjaquez was more of a fight between two Espada than anything else. She tends to cross her arms when not engaged in combat.

In contrast to the majority of her fellow Espada, Harribel is calm, level-headed and analytical, preferring not to engage in combat; she is content on silently observing both parties until the fighting reaches its conclusion, and refuses to fight unless she or her Fracción are challenged or ordered by her superiors (excluding Barragan, sharing her history with him). She strongly opposes the notion of killing, having too many of her friends died in vain.

Before Ichigo Kurosaki and his friends broke into Las Noches, Harribel is seen in the company of Aizen and her fellow Espada - in Aizen's throne room, the debriefing room, and the room which houses the Hōgyoku. However, she, like the other Espada, has her own quarters. Whenever she is present, Aizen usually greets the group with words such as "ladies and gentlemen of the Espada" or "brothers and sisters", apparently for her exclusive benefit, as she is the only female. She views Aizen and his powers in high regard, which is reciprocated by Aizen to a certain extent, as he seems unconcerned with the prospect of his top three Espada fighting a numerically-superior force led by six Shinigami captains without his aid.

However, when she is betrayed by Aizen, Harribel angrily attacks him, showing that Harribel can be quite aggressive and brutal at times, something that wasn't present during her previous fights with Hitsugaya, Lisa, and Hiyori. Harribel's gender and associated rank in the Espada often draws the unwanted attention of other people; Nnoitra Jiruga attempts to provoke her into attacking him with a sharply-worded comment during the Espada meeting. She also catches the eye of Captain Shunsui Kyōraku, even to the point of him mentioning his (rather positive) opinion of her abilities to his opponent.

Strangely, Harribel seems to show some concern for her enemies. This was hinted when she observed Ichigo's fight with Grimmjow and was finalized when she asked Hitsugaya about his fluctuating reiatsu during their fight. Unlike most of her comrades, Harribel does care for her Fracción, as she is noticeably upset when she senses their presences fading, and later angrily assaulting Hitsugaya seconds after their defeat at the hands of Captain-Commander Yamamoto.