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Tomonori Iwaki
Injured in an accident when he was five years old, middle-schooler Tomonori has a thing for older women. He's crushed when his homeroom teacher gets engaged, and his disappointment is increased when he finds that he's been married off to Rizel, who appears to be a young girl, by his family. When it comes out that he's got a wife who looks like she should be in grade school, his friends don't seem to know if they should be jealous, or treat him like a pervert.
Supposedly a "national treasure"--the first human composed of nanomachines, Rizel is totally devoted to the hapless Tomonori. She does everything she can to win his affection in a cute and charming way, but she can go a little out of control if her feelings get hurt. Her past and her actual identity are a mystery.
Aoi Seimoto
Tomonori's cute female classmate. They have a friendly relationship, but no romance (she's too young for him). She attempts to teach Rizel the way to win a man's heart through having her read shojo manga. (specifically, "D.N. Angel" :-) )
Papa 1, 2 & 3
Rizel's Papas apparently are government agents, but they are wholly devoted to her, go on stakeouts to keep an eye on Tomonori and Rizel's dates, and protect her as best they can.
Rizel's American counterpart, who shows up in Japan to discover the research secrets behind the Protoman Kind project. She and Rizel end up fighting for Tomonori's heart, and their secret ultimate weapons are not what you might have thought...
Ryunosuke Hououin
A rich and somewhat spoiled boy who goes to school with Tomonori. He is snobby, and initially upset that there are no women in his low-class school who attract his attention, but he falls instantly in love with Rizel, much to Tomonori's dismay.

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