In the Kingdom of Windbloom, Arika Yumemiya enrolls at Garderobe Academy to become an Otome—a virgin girl who is able to use a HiME (Highly-advanced Materializing Equipment) that bestows destructive abilities. Arika also wishes to find her mother who was a Meister Otome, an Otome of the highest rank responsible for being the personal bodyguard and super weapon of the specific nation they are assigned to. While attending the academy, Arika makes friends with Nina Wáng, a distinguished Otome student, and Mashiro Blan de Windbloom, the current princess of the kingdom. With them by her side, Arika quickly adjusts to the academy's environment as she spends her days eagerly training, navigating social relationships, and developing her skills as an Otome. However, Arika soon realizes that the process of becoming an Otome is fraught with dangers and unsavory political dealings. Bombarded with numerous personal dilemmas, Arika must make many sacrifices if she truly wishes to achieve her goals.

Picture Drama included in the Blu-Ray release. Arika and Eristin have just transferred to a new school. On their way home they found a wounded lost cat and they decided to look for its owner.

Extra shorts that come after each episode. This entry also includes the Mai Hime vs. Mai Otome - Moe? The Greatest Battle! episode.

Specials that followed on the Mai-Otome DVD.