She was the youngest child of Lieutenant-General Nikolai Fyodorovich Golitsyn (1728-1780) and Princess Praskovia Ivanovna Shuvalova (1734-1802).

After the death of her father, she moved with her mother to the house of her uncle, Ivan Shuvalov, on the corner of Nevsky Prospekt and Malaya Sadovaya.

Golitsyna went on four years of foreign travel, spending much of her time in Paris, but his acquaintances and connections there had nothing to do with literature or the arts.

Promoted to the rank of colonel, he felt no inclination to any military or the civil service, but his strict honesty was noted.

At the same time, the Countess Golovin became closer to the French emigrant Princess de Tarant and under her influence, converted to Roman Catholicism.

In Paris, they were accepted in the high society of Château de Saint-Germain-en-Laye, but the beginning of the Napoleonic wars forced them to return to Russia.

Thanks to the efforts of her husband, on April 9, 1816 Countess Golovin was granted in chevalier's ladies of the Order of St. Catherine (small cross), and her younger daughter as the maid of honor.