In August 1728, Victor Amadeus's consort Anne Marie d'Orléans died after a series of heart attacks. Two years later he married Anna in a private ceremony on 12 August 1730 in the Royal Chapel in Turin, having obtained permission from Pope Clement XII. Victor Amadeus created her Marchesa of Spigno. The title was attached to a fief of the Holy Roman Empire, acquired as spoils of the War of the Spanish Succession and subsequently owned by an illegitimate brother of Victor Amadeus.
The couple made their marriage public on 3 September 1730, much to the dismay of the court. A month later, Victor Amadeus announced his wish to abdicate the throne and did so in a ceremony at the Castle of Rivoli on the day of his marriage. His son succeeded him as Charles Emmanuel III.
Taking the style of King Victor Amadeus, he and Anna moved into the château de Chambéry outside the capital. The couple took a small retinue of servants and Victor Amadeus was kept informed of matters of state. Under the influence of Anna and despite having suffered a stroke in 1731, Victor Amadeus decided he wanted to resume his tenure on the throne and informed his son of his decision. Arrested by his son, he was transported to the Castle of Moncalieri and Anna was taken to a house for reformed prostitutes at the Castle of Ceva but was later allowed to return to the Castle of Rivoli where her husband was moved. She was returned to him on 12 April. The stroke seemed to have affected Victor Amadeus in a way which caused him to later turn violent toward his wife, blaming her for his misfortunes.
King Victor Amadeus having died in September 1732, Anna was imprisoned in the Convent of San Giuseppe di Carignano. She was later moved to the Convent of the Visitation in Pinerolo where she died aged 88. Her son later left the Savoy court in disgrace but succeeded to the marquisate of Spigno. She was buried at Pinerolo in a grave without a headstone.