Troicki was part of Serbia's Davis Cup team that reached the final for the first time in their history in 2010. He was initially overlooked for the singles rubbers, but after compatriot Janko Tipsarević was beaten by Gaël Monfils in straight sets, Troicki was chosen to play the final singles rubber, as well as the doubles. With Serbia and France tied at 2–2, Troicki won the deciding match 6–2, 6–2, 6–3, against Michaël Llodra to clinch Serbia's first Davis Cup, a triumph labeled by national coach Bogdan Obradovic as "the greatest sporting triumph in Serbia's history".