Golitsyn fought bravely during the Napoleonic Wars. In 1805, during the War of the Third Coalition, his regiment started the campaign in the corps of Count Bennigsen in Silesia. In December 1806 he led the 4th division at the Battle of Golymin. This victory and success of Bennigsen at the Battle of Pułtusk stopped the French forces. After that, Golitsyn commanded the cavalry of the left wing. His forces took part in all major actions – at Eylau, Heilsberg and Friedland. For this campaign he received numerous Russian and foreign awards: the Order of St. George 3rd class (on 21 January 1807), the Order of St. Vladimir 2nd class, the Prussian Order of the Red Eagle (on 18 May 1807), the Order of the Black Eagle (on 25 June 1807), and a gold sword with diamonds with the inscription "For Bravery."