Marie was born on 17 September 1799, the eldest child of Duke Alexander of Württemberg and his wife Princess Antoinette of Saxe-Coburg-Saalfeld.

The Kingdom of Württemberg, as it was known from 1806 onward, was a prominent entity in Germany on the level of Prussia, Bavaria, and Saxony, with connections to the English and Russian royal families.

As her father was a general in the Russian army, and later governor of Belarus, Marie lived from 1802 to 1832 at Jelgava (modern day Latvia) and in a St. Petersburg palace.

While Ernest initially sought a wife of high status, he found that his age and poor reputation limited his choices.

[2][3] As a result of this union, Marie became stepmother of Ernest II and Prince Albert, future husband of Queen Victoria of the United Kingdom.

[2][3] By 1843 Marie had adopted a child of "humble parentage", though Albert cautioned her to avoid giving it[clarification needed] hopeless aspirations to rank.