Henriette was born about 1383, the eldest of three daughters of Henri II de Montfauçon, seigneur d'Orbe, Echallens and Bottensen, and Marie de Châtillon, vicomtesse de Blaigny. Her father died at the Battle of Nicopolis in October 1396, a year before the death of his father Etienne. She had no legitimate brothers, though her father had three illegitimate children.
On 13 November 1397 Eberhard III 'der Milde', Graf von Württemberg, completed a marriage contract for his son Eberhard IV and Henriette. In this way he assumed the rule over Mömpelgard and related estates, which he passed over to Eberhard IV in 1407. Mömpelgard remained part of Württemberg until 1802.
Henriette and Eberhard had three children, Anna, Ludwig I and Ulrich V, who would all have progeny. After Eberhard's death in 1419, Henriette became guardian of her sons together with councillors from the government of Württemberg. At the end of 1421 Henriette withdrew from the rule of Württemberg, but continued to rule Mömpelgard until her death on 14 February 1444 at Montbéliard in Mömpelgard.