Anna spent her childhood at Staniszów Castle in Silesia.
She was artistically talented and in 1862 she went to Berlin, where she received painting and music lessons and met Count Otto of Stolberg-Wernigerode, whom she married on 22 August 1863 at Staniszów Castle.
His political rise allowed a major expansion of Wernigerode Castle, which lasted from 1862 to 1893.
The castle was restructured in a historicistic style; Anna was creatively involved in this endeavour.
She and her daughters and daughters-in-law created the eight large tapestries in the Castle Church.