She married the Duke of Courland, Peter von Biron, on March 6, 1774, in Mitau.

Yevdokiya Yusupova was the eldest daughter of Prince Boris Grigoryevich Yusupov and Irina Mikhaylovna Zinovyeva.

[1] Duke Peter was described as wild, and Yevdokiya Yusupova was regarded as a beauty with spiritual qualities.

[3] The relationship between Yusupova and Peter soon deteriorated, however, and she wished to be freed from the abuse he is reported to have treated her with.

After having attended the wedding of Tsesarevich Paul to Maria Feodorovna (Sophie Dorothea of Württemberg) on 26 September 1776, she refused to return to Mitau.