Usui Takumi (碓氷 拓海 , Takumi Usui)

One of the most popular boys at Seika High, Usui appears to take little interest in anything and prefers to observe things as they unfold, though proves to be extraordinarily talented in numerous areas. He develops an interest in Misaki and is the first to learn she is working at a maid café, but chooses to keep her secret. He tends to tell Misaki he likes her, but she dismisses his behavior simply as harassment. Still, he continues to watch over and protect her, as well as offering insightful advice on how to deal with the boys at Seika effectively. Even though he says he likes Misaki, he tells Kanou that he doesn't want to be in a serious relationship.

Misaki Ayuzawa (鮎沢 美咲 ,Ayuzawa Misaki)

The protagonist of the story, Misaki is the first female Student Council President at Seika High and known for her extremely demanding and aggressive attitude towards boys and relentlessly reforming them to what she considers are acceptable standards of behavior. Her negative attitude towards males is mostly attributed to her father amassing with a huge debt and then disappearing; Misaki became determined to make sure her weak mother would not have to work so hard to support both Misaki and her younger sister. To this extent, she secretly and reluctantly works as a maid at Café Latte. Regardless of her endeavors, Misaki is always driven to her best and has a strong sense of justice, but has a tendency to forget her own well being in the process when she is helping others. She starts to have feelings for Usui as the series progresses, although she doesn't realize them herself.

Kaichō wa Maid-sama!

Once an all boys school, Seika High, a renowned school full of reckless and filthy students, has recently become a co-ed school. However, with the female population still remaining a minority even after the change over the recent years, Misaki Ayuzawa takes it into her own hands to reform the school and allow a chance for the girls to feel safer in the rough environment.

Training, studying and even becoming the first female student council president of the school, Misaki has gained a reputation among the male students body as an uptight boy-hating dictator and as a shining hope for the teachers and fellow female students. However, despite her tough-as-nails appearance, she secretly works part-time at a maid cafe in order to support her family. Unfortunately, her secret is soon revealed when the somewhat impassive Usui Takumi, a popular boy at school, nonchalantly discovers her in a maid uniform after school.