Born in Stuttgart, she was the youngest of twelve children born from the marriage of Christoph, Duke of Württemberg and Anna Maria of Brandenburg-Ansbach.

From her eleven older siblings, nine survive adulthood: Eberhard, Hereditary Prince of Württemberg, Hedwig (by marriage Landgravine of Hesse-Marburg), Elisabeth (by her two marriages Countess of Henneberg-Schleusingen and Countess Palatine of Veldenz-Lauterecken), Sabine (by marriage Landgravine of Hesse-Kassel), Emilie (by marriage Countess Palatine of Simmern-Sponheim), Eleonore (by her two marriages Princess of Anhalt and Landgravine of Hesse-Darmstadt), Louis III, Duke of Württemberg, Dorothea Maria (by marriage Countess Palatine of Sulzbach) and Anna (by her two marriages Duchess of Oława and Legnica).

In Weimar on 5 May 1583 Sophie married Frederick William I, Duke of Saxe-Weimar.

They had six children, of whom only two survive adulthood: Sophie died in Vacha aged 26, following complications of her last childbirth.

She was buried in the Stadtkirche St. Peter und Paul, Weimar.