Grand Duchess Olga of Russia was born on 11 September 1822 in St. Petersburg, Russia. Her father was Emperor Nicholas I of Russia. Her mother was Empress Alexandra of Russia (née Princess Charlotte of Prussia), the daughter of King Frederick William III of Prussia and Queen Louise of Prussia.

Olga grew up as part of a close family of eight sisters and brothers. Attractive, cultured and intelligent, she was considered to be one of the most eligible princesses in Europe. She spoke several languages, and was fond of music and painting.

Olga met Crown Prince Charles of Württemberg in early 1846 in Palermo, Two Sicilies. Her parents wished that she make a dynastic marriage, especially since her siblings Alexander, Maria and Alexandra had married relatively insignificant royal partners.
The wedding was held in great splendor on 13 July 1846 at the Peterhof Palace, Russia.

The couple had no children, probably because of Charles’ homosexuality. In 1863, Olga and Charles adopted Olga's niece, Grand Duchess Vera of Russia, the daughter of Olga’s brother Grand Duke Constantine.

On 25 June 1864, after the death of his father, Charles acceded the throne and became the third king of Württemberg, making Olga the fourth queen of Württemberg.

With no children of her own, Olga dedicated her life to social causes. These charitable enterprises made her very popular among her subjects, much more so than her husband.

Olga was noted for her dignity and queenly demeanor. On a visit by the royal couple to Austria in July, 1873, a lady-in-waiting to Empress Elisabeth of Austria noted, "He is most insignificant. She makes a most imposing appearance ... the only one who is a queen ..."

When her husband died on 6 October 1891, Olga became Queen Dowager of Württemberg. She died one year later, on 30 October 1892 in Friedrichshafen, at 70.

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