Go Won-hee debuted in the entertainment industry in 2011 as a commercial model. In 2012, she became the youngest model for Asiana Airlines. She was originally set to debut as a member of the girl group Fiestar but eventually pursued acting instead. Her first acting projects include the 2011 film A Sailor Went to Sea and the 2012 two-part cable TV movie Natural Burials. In 2015, she was nominated for an Excellence Award at the KBS Drama Awards for her performance in the series The Stars Are Shining. That same year, she became part of the sixth season of the sketch comedy-variety program Saturday Night Live Korea. In 2017, she was named Best New Actress at the 10th Korea Drama Awards for the KBS2 series Strongest Deliveryman. In 2019, she landed her first primetime leading role in the KBS2 fantasy romantic comedy Perfume, opposite Shin Sung-rok. She was nominated for an Excellence Award at the 2019 KBS Drama Awards for her work in the series.

In June 2016, Go Won-hee confirmed her relationship with her The Stars Are Shining co-star Lee Ha-yool. However, the two broke up after three years of dating. In October 2022, she married her non-celebrity boyfriend in a private ceremony in Seoul.