Frederick was born in Dessau on 23 September 1799 as the fourth (but third surviving son) of Frederick, Hereditary Prince of Anhalt-Dessau, by his wife Landgravine Amalie of Hesse-Homburg, daughter of Frederick V, Landgrave of Hesse-Homburg.

In Rumpenheim Castle in Offenbach am Main on 11 September 1832, Frederick Augustus married Princess Marie Luise Charlotte of Hesse-Kassel (b. Copenhagen, 9 May 1814 – d. Schloss Hohenburg, 28 July 1895).

She was a daughter of Prince William of Hesse-Kassel by his wife Princess Louise Charlotte of Denmark, a sister of King Christian VIII of Denmark.

Marie was an older sister of the later Queen Louise, wife of King Christian IX of Denmark.

Princess Marie survived him by 30 years and died on 28 July 1895 in Schloss Hohenburg in Lenggries in Bavaria.