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Daioh chronicles the everyday life in an unnamed Japanese high school of six girls and two of their teachers: child prodigy Chiyo Mihama and her struggle to fit in with girls five years older, reserved Sakaki and her obsession with the cute animals who seem to hate her, spacey Ayumu “Osaka” Kasuga with a skewed perspective on the world, Koyomi “Yomi” Mizuhara’s aggravation at an annoying best friend, Tomo Takino, whose energy is rivaled only by her lack of sense, sporty Kagura and her one-sided rivalry with Sakaki, and their homeroom teacher Yukari Tanizaki and her friend, physical education teacher Minamo Kurosawa. Secondary characters include Kimura-sensei, a creepy male teacher with an obsession with teenage girls, and Kaorin, a classmate with a crush on Sakaki.
The story covers three years of tests, talking between classes, culture festivals, and athletic events at school, as well as time spent traveling to and from school, studying at Chiyo’s house, and vacations spent at Chiyo’s summer beach home and the fictional theme park Magical Land, concluding with the graduation of the main cast. It is generally realistic in tone, marked by occasional bursts of surrealism and absurdity, such as Osaka imagining Chiyo’s ponytails being “unscrewed” from her head and an episode featuring the characters’ New Year’s dreams.