"With mutual love and respect, we have made the decision to separate as a couple. We are grateful for the friendship that we have and will continue to have," they said in a joint statement to ET on Thursday.
The pair -- who were last seen together at the Oscars in March 2018 -- met at a Bachelor viewing party in 2011 and married in September 2015.
Williams and Van Veen, co-founder of CollegeHumor and Vimeo, tied the knot in a ceremony officiated by Tom Hanks at Brush Creek Ranch in Saratoga, Wyoming. The actress' father, Brian Williams, walked her down the aisle, with stars like Lena Dunham, John Mayer, Zosia Mamet, Jemima Kirke, Seth Meyers and Katy Perry in attendance. The couple had been private about their romance in the public eye.
Van Veen and Williams' split comes weeks after news broke that Bradley Cooper and Irina Shayk had gone their separate ways after four years together. See more in the video below.