After appearing in a Johnson & Johnson advertisement in 1990, Jeon Do-yeon made her acting debut in the 1992 TV series Our Heaven 2. In 1997, she landed her first big screen role in the movie The Contact. She picked up several acting citations for her performance in the movie, including Best New Actress trophies at the 35th Grand Bell Awards and the 18th Blue Dragon Film Awards. In 1999, she took home her first Baeksang Best Actress trophy for the melodrama movie A Promise. In 2001, she was once again named Best Actress at the Baeksang Arts Awards for the film I Wish I Had a Wife. In 2005, she showcased her award-winning acting chops anew in the movie You Are My Sunshine, where she played the role of a prostitute who contracts AIDS. That same year, she won the Daesang at the SBS Drama Awards for the romantic series Lovers in Prague. In 2007, Jeon Do-yeon was chosen as the 60th Cannes Film Festival Best Actress for her performance in the melodrama Secret Sunshine, making her the first ever Korean to achieve such feat. In 2016 and 2020, she collected her third and fourth Baeksang Best Actress wins for the movies The Shameless and Birthday, respectively.

On March 11, 2007, Jeon Do-yeon married businessman and professional car racer Kang Shi-kyu. They welcomed their daughter on January 22, 2009.