Dolgopolov represented Ukraine alongside Elina Svitolina at the 2016 Hopman Cup. He won his singles matches against Jack Sock, Jiří Veselý and Lleyton Hewitt. He and Svitolina were the winners of their group in the round robin phase, and went into the final against the Australia Green team. Dolgopolov lost to Nick Kyrgios 3–6, 4–6. The Ukrainian team were the runners-up of the tournament.