The show is based on the well-known British series about a group of women struggling to deal with illicit relationships. The original series starred Sarah Parish, Sharon Small, Shelley Conn, and Orla Brady.
Deadline reports that Kim has joined the programme as one of the four leads, with Rochelle Aytes and Jes Macallan already cast.
She will play Katie, a therapist who was having an affair with one of her patients before his death, and who later becomes romantically entangled with her late patient's son, played by Erik Stocklin.
Since Lost, Kim has married her longtime boyfriend Jeong Hyeok Park and starred in a handful of South Korean films.
This will be Kim's first return to television since the end of Lost, in which she played Sun-Hwa Kwon.
Mistresses is scheduled to launch in the summer of 2013.