She was the second wife of Jogaila (Władysław II Jagiełło), King of Poland and Supreme Duke of Lithuania (reigned 1387–1434).

Their marriage was politically motivated to strengthen Jogaila's ties with the Piast dynasty and his claims to the Polish throne.

Their marriage was rather distant and during fourteen years Anna bore only one daughter, Hedwig Jagiellon, who died without issue.

It is likely that Anna was born in Celje Castle (in the Duchy of Styria, now in Slovenia), which was ruled by her father William and his cousin Herman II.

[1] Jogaila's first wife and reigning Queen Jadwiga of Poland, Anna's second cousin, died in July 1399 after childbirth complications.

Klemens Moskarzewski, Castellan of Wiślica, accused the queen of marital infidelity with Jakub Kobylański and Mikołaj Chrząstowski.

A year later, Jogaila accused Anna of an affair with Jędrzej Tęczyński, but that case did not reach a public hearing.

It was not a male heir desired by Jogaila or Polish nobles, but it still strengthened Anna's position and she became a little more visible in politics.

[9] In February 1412, Anna and Jogaila hosted the wedding of Ernest, Duke of Austria, and Cymburgis of Masovia.

Anna met with Barbara of Cilli, Sigismund's wife and daughter of Herman II – the girls grew up together.

[12] In early 1413, Anna's five-year-old daughter Hedwig was officially proclaimed heir presumptive to the Polish throne during a congress in Jedlnia.