Sophie was born in Stuttgart; her parents were King William I of Württemberg and Grand Duchess Catherine Pavlovna of Russia, the fourth eldest daughter of Tsar Paul I.

[2] When she was sixteen, she and her sister were taken by their father on an educational trip to Italy,[2] which was otherwise customary for upper class males.

[2] Through her progressive father, Sophie came in contact with liberal ideas from her early youth and supported democracy rather than royal absolutism.

[2] Sophie married her maternal first cousin, the future Prince of Orange (later King William III), in Stuttgart on 18 June 1839 with the idea that she would in the end succeed in dominating him, or so her mother-in-law Anna Pavlovna thought.

Her father, while being a liberal progressive in other aspects, still favored dynastic marriages and wished for his daughters to marry monarchs.

Prior to her marriage, King Otto of Greece and Duke William of Brunswick were possible suitors for Princess Sophie.

The engagement with the first came to nothing because Princess Sophie's ambitious father had no confidence in the newly established Greek monarchy of Otto.

Sophie did not wish to live with her husband and devoted herself to her children (as far as she was allowed), charity, cultivating her own intellectual interests and the private study of various subjects.

The relationship between Sophie and William did not improve even after they became king and queen, and they continued to be in a state of constant conflict.

[2] Sophie was to fulfill her representational duties as queen in public, but allowed to live her private life as she wished.

[2] She regularly visited her father, who remained her advisor and confidant until his death, after which he was succeeded by her friend George Villiers, Lord Clarendon (1800–1870), with whom she corresponded.

[2] She participated in the public debate and published an article in the famous Revue des Deux Mondes, in which she argued that the royal houses must keep up with the times.