Chihiro Kawashima holds the position of vice principal at Waldstein Academy and is a secondary character in the story. Her physical appearance is distinctive and bold. She is a tall woman with fair skin and a somewhat muscular build, possessing brown eyes and long, unusual brown hair styled with bangs and a dango braid. Her fashion sense leans towards the flamboyant; she often wears large earrings, a white dress, a purple jacket, and matching purple heels, and is known for applying a generous amount of pink lipstick to her large lips. Her natural voice has a somewhat thick quality, but it notably shifts to a higher, more tender pitch when she interacts with a specific person.

In terms of personality, Chihiro generally presents herself as a responsible and serious administrator. However, this demeanor is famously contradicted by her behavior regarding Fumiaki Uchida. Her infatuation with Uchida begins after he pays her an unexpected compliment on her hairstyle, an aspect of her appearance that is often ridiculed by students. This single event triggers an intense and obsessive romantic fixation. She documents her feelings in a love diary, spies on him, becomes extremely possessive and jealous, especially of Mikaze who is Uchida's main love interest, and makes repeated, often unsuccessful, attempts to win his affection, including trying to kiss him and bringing him lunch. Her feelings are visually represented in the anime by pink hearts appearing in her eyes whenever she sees Uchida.

Before this infatuation becomes apparent, Chihiro is initially hinted to be a potential antagonist, partly due to her secretive nature and knowledge surrounding the death of the academy's principal. It is eventually revealed that her true role is quite the opposite. She is a powerful white mage whose primary mission, undertaken at the request of the late principal Junichiro Kumashiro, is to protect his daughter, Maya Kumashiro. She demonstrates unwavering loyalty and deep respect for Maya, following her orders diligently and becoming easily upset when anyone bothers her. This loyalty extends to her magical duties, which include creating a fake body for Maya and having previously done the same for Maya's father.

Chihiro's magical abilities are significant, marking her as one of the physically and magically strongest characters. As a white mage, her powers are more defensive in nature compared to the offensive magic of a black mage like her rival, Mikaze. Her skills include erecting powerful barriers, materializing beams of light for offensive purposes, and demonstrating notable healing abilities, such as curing Uchida after he was frozen in time. Even in her untransformed state, she exhibits impressive physical strength and can use her earrings as flash grenades.

Her key relationships define much of her role. Her devotion to Maya Kumashiro is a core aspect of her character, serving as a professional and loyal supporter. Her violent hatred for Mikaze is fueled by jealousy over Uchida's affections, although it is later implied that the two have a deeper, unrecognized history, as Mikaze identifies Chihiro as the White Witch. Her relationship with Uchida is the primary driver of her comedic and dramatic development. While her attempts to seduce him fail in the main timeline, her feelings are genuine, and she ultimately sacrifices her life to protect Maya and Uchida from Mikaze. In alternative continuities, such as the manga, she survives, and with the alien invasion that led to Uchida's death being averted, it is implied that she may marry him.