De Gouw moved to Sydney in order to have a greater opportunity for acting roles. She appeared in a number of TV series, mostly in guest starring roles. In 2012, she debuted in the film Kath & Kimderella as Isabella, Kath and Kim's maid. She moved to Los Angeles later that year and landed the recurring role of the Helena Bertinelli/The Huntress in the action-adventure series, Arrow. In 2013, De Gouw was cast in the NBC series Dracula as Mina Murray alongside Jonathan Rhys Meyers and Oliver Jackson-Cohen. The series lasted only 10 episodes, and NBC announced on 9 May 2014 that the show would not be renewed for another season. In 2016, De Gouw was cast as fictional abolitionist Elizabeth Hawkes in the WGN series, Underground. She played the lead role Ren Amari in the 2017 feature film OtherLife based on the novel Solitaire by Kelley Eskridge.