Frederica was born on 27 July 1765 in Treptow an der Rega, Farther Pomerania (now Trzebiatów, Poland) as the seventh child and second daughter of Frederick II Eugene, Duke of Württemberg and Friederike Dorothea of Brandenburg-Schwedt.

[1] She was the sibling of King Frederick of Württemberg, Sophia Dorothea, Empress of Russia, and Elisabeth, Archduchess of Austria.

On 6 June 1781, Frederica married Prince Peter Frederick of Holstein-Gottorp.

Her sister Sophia Dorothea encouraged the marriage, and her brother-in-law Paul I became the godfather of her sons.

He would succeed his cousin William as Grand Duke of Oldenburg in 1823, many years after Frederica's death.