Anne was the third child of René, Duke of Alençon and his second wife Margaret of Lorraine,[1] daughter of Frederick, Count of Vaudémont and Yolande of Anjou.

She was betrothed to William IX, Marquis of Montferrat of the Palaiologos family in 1501 and married him on 31 October 1508, the day after her sixteenth birthday, in the church of St. Sauveur in Blois.

She remained involved in the government of Montferrat when Boniface was succeeded as Marquis by her brother-in-law John George, previously commendatory abbot of Lucedio and (unconsecrated) Bishop of Casale.

A dispute over the succession to the Marquisate, an imperial fiefdom, ensued, the contenders being the Gonzaga, the Marquis of Saluzzo and the House of Savoy, all of whom were able to make plausible claims.

On retiring from public life Anne d'Alençon entered the convent of Dominican Sisters of Catherine of Siena which adjoined her palazzo in Casale Monferrato.