George II was a son of the Duke Louis Frederick of Württemberg-Montbéliard (1586–1631) from his second marriage to Anna Eleanor (1602–1685), daughter of Count John Casimir of Nassau-Gleiberg (1577–1602).

King Louis XIV was trying to conquer all Württemberg possessions on the left bank of the Rhine.

[clarification needed] In 1684, he was given an opportunity to return, under the condition that he recognized the King of France as his liege lord.

He refused, and Württemberg-Montbéliard was administered by his cousin Frederick Charles, Duke of Württemberg-Winnental until 1698.

Together, they were the parents of the following children: George II died on 1 June 1699 in Montbéliard and was succeeded by his only surviving son, Leopold.