Moon Chae-won made her acting debut in the SBS series Mackerel Run in 2007. Her career breakthrough came the following year when she played a gisaeng in the SBS sageuk The Painter of Wind. Her work in the series won her the New Star Award at the SBS Drama Awards. Moon Chae-won and Moon Geun-young also made history as the first female stars to win the Best Couple Award for the series. In 2011, she headlined the well-received KBS2 sageuk The Princess’s Man, which scored her a Top Excellence Award at the KBS Drama Awards. That same year, she starred in the film War of the Arrows, which earned her Best New Actress trophies at the 48th Grand Bell Awards and the 32nd Blue Dragon Film Awards. In 2012, she was paired with Song Joong-ki in the KBS2 melodrama Nice Guy, in which she bagged a Top Excellence Award at the KBS Drama Awards. In 2013, she acted alongside Joo Won in the KBS2 medical drama Good Doctor, which gave her an Excellence Award at the KBS Drama Awards.

Moon Chae-won got accepted into the Western Painting program of the Chugye University for the Arts. However, she dropped out in 2006 to become an actress.