Olga met Kronprinz Karl 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.

Olga gave her consent to Karl's proposal of marriage after only a few meetings, on 18 January.

The couple had no children, probably not because of Karl's homosexuality, which he lived openly in his later age, but of his other health problems.

She was especially interested in the education of girls, and also supported wounded veterans and the disabled assisted in part by philanthropist Charlotte Wahl of Stuttgart.

Olga was fond of agriculture and was keenly interested in all happenings on her farming estate which was located in the German Volhynia colony of Russia.

A series of massive rock formations was discovered by the British-born Australian explorer Ernest Giles in central Australia in 1872.

The entire geological formation then became known as "The Olgas", before the indigenous name "Kata Tjuta" was officially proclaimed in the 1980s.

On a visit by the royal couple to Austria-Hungary 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 ..."[2] In 1881, Olga wrote a memoir called Traum der Jugend goldener Stern (translated as The Golden Dream of My Youth) which described her childhood at the Russian Imperial Court, her grief at the loss of her sister Alexandra, and her early adult life, ending with her wedding to Karl.