In 1774 Golitsyn was enrolled in the Leib Guard Preobrazhensky regiment and received his first rank of sergeant in 1777. He continued his education in Strasbourg in 1782. He travelled in Germany and France with the family. In 1786 the Golitsyns settled in Paris, where Dmitry and his brother Boris studied military science at the École Militaire. On 14 July 1789 Dmitry was somehow involved in the Storming of the Bastille. He wrote his mother about the activities of the National Assembly (France). In 1791 the Golitsyns returned to Imperial Russia and he entered the cavalry. During the Kościuszko Uprising he fought under Aleksandr Suvorov and on 24 October 1794 distinguished himself at the Battle of Praga and earned his first Order of St. George of the 4th degree.