Born in Warsaw, she was the eldest child and only daughter of John II Casimir Vasa, King of Poland and Grand Duke of Lithuania, by his wife Marie Louise Gonzaga.

The solemn baptism of the Princess took place on 2 August 1650 in St. John's Cathedral in Warsaw, her birthplace.

Her godparents were Ferdinand III, Holy Roman Emperor (for whom Prince Karol Ferdynand Vasa stood proxy) and his recently new consort Eleonora Gonzaga (for whom the Princess Theodora Christine Sapieha stood proxy), and Pope Innocent X (represented by Nuncio Giovanni de Torres).

Since her birth, Maria Anna was destined to enter in the Carmelite Order, since her parents were devoted Catholics and planned this for her.

Maria Anna's funeral took place on 12 August 1651 in the Church of the Carmelite sisters in Warsaw.