Park Ki-woong entered the entertainment industry by appearing in the music video of K2’s song Giving You Love in 2004. In 2007, he led the romantic comedy film My Tutor Friend 2, opposite Lee Chung-ah. In 2009, he was nominated for Best New Actor at the KBS Drama Awards for his performance in Story of a Man and Invincible Lee Pyeong-gang. In 2012, he became part of the main cast of the KBS2 period drama Gaksital, which won him Best Supporting Actor at the KBS Drama Awards. In 2016, he appeared in the MBC series Monster, in which he was nominated for an Excellence Award at the MBC Drama Awards. In 2018, he took home the Best Character trophy at the SBS Drama Awards for his work in the legal mystery-thriller Return. In 2019 and 2020, he received back-to-back Excellence Award nominations at the MBC Drama Awards for Rookie Historian Gu Hae-ryung and Old School Intern.

Park Ki-woong enlisted for his mandatory military service on May 8, 2014. He was discharged on February 7, 2016. He majored in visual design at the Daejin University and in March 2021, he officially debuted as a painter.