Her father Count Fyodor Rostopchin was lieutenant-general and, later, Minister of Foreign Affairs for Russia.

While facts concerning the origin of the great fire of Moscow are disputed by historians, Sophie Rostopchine's father has been said by some to have organized (despite opposition from the wealthy property-owners in the city) the great fire which forced Napoleon to make a disastrous retreat.

In 1814 the Rostopchine family left Imperial Russia for exile, going first to the Duchy of Warsaw, then to the German Confederation and the Italian peninsula and finally in 1817 to France under the Bourbon Restoration.

In France, the father established a salon, and his wife and daughter converted to Roman Catholicism from Russian Orthodoxy.

The marriage was largely an unhappy one: her husband was flighty, distant and poor (until being made a Peer of France in 1830), and his infrequent conjugal visits to their château des Nouettes (near L'Aigle, Orne) produced eight children, including Nathalie de Ségur and the father of the historian Pierre de Ségur (Eugène de Ségur is said to have called his wife "la mère Gigogne", or "Mother Gigogne" in reference to a theatre character of 1602, an enormous woman out of whose skirts a crowd of children appeared).