Kawakami debuted 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 Shindou) and Sgt. Frog (Fuyuki Hinata).

A versatile seiyu, Kawakami is capable of providing voice for a wide range of characters from young boys (Hikaru Shindo, Fuyuki Hinata, Chiriko), cute girls (Sugar, Misuzu Kamio, Sayuri Kurata) and comical characters (Ai Mori, Pirika). But the most known genre of her roles are tomboyish characters (Soifon, Utena Tenjou). With such a powerful voice, she is often affiliated in paranormal and shoujo-ai-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 August 2008, Kawakami became sick, requiring surgery. As a result, she has taken a 10 month sick leave. During this time, her ongoing roles having been replaced by the following seiyu:

- H?ko Kuwashima: Bleach (Soifon), Sgt. Frog (Fuyuki Hinata)
- Satsuki Yukino: Pok?mon (Pokedex)?
- Yumi Kakazu: Tales of VS (Nanaly Fletch)