Baek Ji-won debuted as a theater actress in 1996 before expanding her acting career to the screen. In 2003, she became part of the omnibus film If You Were Me, which was followed by a role in the movie Solace in 2006. In 2015, she appeared in the SBS weekend drama I Have a Lover as Ji Jin-hee’s half-sister. In 2017, she was cast in multiple TV series such as My Golden Life and Mad Dog, which both aired on KBS2. In 2019, she played a nun in the SBS comedy-drama The Fiery Priest, which won the Best Supporting Team citation at the SBS Drama Awards. She also received an Excellence Award nomination for her work in the series. In 2020, she was nominated for Best Supporting Actress at the KBS Drama Awards for Once Again and How to Buy a Friend. That same year, she joined the SBS series Do You Like Brahms, which starred Park Eun-bin and Kim Min-jae. In 2022, she reunited with Park Eun-bin in the hit ENA legal drama Extraordinary Attorney Woo.

Baek Ji-won attended Kyung Hee University.