Homura Akemi wore them when she's a civilian and a Magical Girl (till the 3rd loop) , Mirai Wakaba also use them, but she somehow disposed it after she became a Puella Magi, while her
fiancee friend Saki Asami, currently wears them in civilian & Puella Magi modes.
Hilda Adams had owned a pair of glasses before she had healed her eyes with magic.She occasionally (but not frequently) uses them for reading stuff. Jinna Asumi also uses them, trying to read several complex words. But she's still illiterate.
- And no, wearing them does not make you smarter. Unless you want to stereotype hard.