After graduating from the University of Paris in 1862, between 1864 and 1867 he served as a clerical officer at the Ministry of Foreign Affairs.

Later in the 1870s he participated in an archaeological expedition in Vladimir Directorate that discovered several Stone Age sites.

In recognition for this work, in 1877 Golitsyn was elected as a corresponding member of the Moscow Archaeological Society [fr; ru; uk].

In the 1880s he established the production of sparkling wines using the classical French technology of direct fermentation in bottles.

In Crimea, Golitsyn became an avid collector of 17th–20th century wines, eventually accumulating around 50,000 bottles.