Do Ji-won began her entertainment career as a cosmetics model before transitioning into acting. In 1990, she appeared in the KBS2 series Seoul Ddukbaegi, which won her Best New Actress at the KBS Drama Awards. She rose to prominence in 2001 when she joined the SBS sageuk Ladies of the Palace, which earned her a Top Excellence Award at the SBS Drama Awards. In 2010, she starred alongside Ji Chang-wook in the hit KBS1 daily series Smile, Dong-hae, which gave her an Excellence Award at the KBS Drama Awards. In 2015, she played one of the main characters in KBS2’s Unkind Women. In 2017, she became part of the KBS2 sageuk Seven Day Queen and the SBS family drama Bravo My Life. In 2019, she worked with Shin Hye-sun and L in the KBS2 fantasy romance Angel’s Last Mission: Love.

Do Ji-won majored in dance at Hanyang University. In 1998, she was kidnapped by a man and a woman at a sports center’s parking lot in Seoul. The assailants extorted ₩14 million from her in exchange for her freedom.