Kawakami debuted in 1994 as a role of a boy in Metal Fighter Miku. Her first regular performance was in 1995 as Chiriko in Fushigi Yuugi. Two years after, she landed her first starring voice role as Utena Tenjou in Revolutionary Girl Utena. Aside from Chiriko and Utena, her famous roles are in Air (Misuzu Kamio), Bleach (Soifon), Chrono Crusade (Rosette Christopher), Hikaru no Go (Hikaru Shindo), Sgt. Frog (Fuyuki Hinata), Ape Escape (Natsumi),Yukiko Kawasaki (Dear Boys), Sugar (A Little Snow Fairy Sugar), Aria (Athena Glory), and Miu Fūrinji (Kenichi: The Mightiest Disciple).
Kawakami provided voices for young boys, girls and comical characters. The best-known genre of her roles are tomboyish characters (Soifon, Utena Tenjou). With such a powerful voice, she was often affiliated in paranormal and yuri-themed anime. She also made her name voicing the heroine in the Harukanaru Toki no Naka de series, based from the Neoromance game with the same title produced by Koei in 2000.