Anna was described as attractive and intelligent. She acquired the confidence and love of the introvert Sigismund, and their relationship was described as a happy one, with her functioning as his support during the many trials of the politically unstable 1590s.
Sigismund became King of Sweden as well in 1592, and the king and queen were required to go to Sweden to be crowned. The Poles did not want Sigismund to leave Poland, and demanded that Anna remain in Poland as a hostage. Sigismund rejected this condition, and they departed for Sweden in 1593.
The voyage to Sweden was difficult, and Anne was pregnant. Anne did not like Sweden, nor did she make a good impression on the Swedes: raised as a fervent Catholic, she strongly disapproved of the Protestant Swedes, whom she regarded as heretics, and could not tolerate the Lutheran clergy.
She became involved in a conflict with the Protestant Dowager Queen Gunilla Bielke, whom she accused of having stolen valuables from the Royal Palace. She felt a strong mistrust toward her husband’s Swedish Protestant uncle, Duke Charles. She was crowned as the Queen of Sweden in Uppsala Cathedral on February 19, 1594, but because the ceremony was a Protestant one, she viewed it as an empty ceremony of no consequence.
Her political influence as the confidant of Sigismund was noted, and Anne and her Jesuit confessor Sigismund Ehrenhöffer acted as a channel between the king and the Papal envoy Germanico Malaspina, to whom they gave information about the king’s policy.
In April 1594 in Stockholm, she gave birth to daughter, Catherine, whose baptism was elaborately celebrated at the Swedish court, but the child died soon after.
The Poles had demanded that she leave her daughter Anna Maria behind her as hostage in Poland during their stay in Sweden. She had also been afraid that the Swedes would demand to keep her daughter Catherine (born in Sweden) when she returned to Poland.
On her departure from Sweden in July 1594, she was granted the towns of Linköping, Söderköping, and Stegeborg as personal domains on the condition that she respect the Protestant belief within these fiefs.
Upon their return to Poland, Anne acted as the confidant of Sigismund. She advised him on navigating between the Polish noble factions, on the League against the Ottoman Empire, and especially on the relationship between Poland and the Habsburg dynasty.
She had however no interest in maintaining the personal union between Catholic Poland and Protestant Sweden, and used her influence to oppose the plan to have her son Wladislaus succeed Sweden by sending him there to be brought up a Protestant.
Anne died on February 10, 1598 in Warsaw as a result of haemorrhage during the birth of her last child, who also died then. Sigismund III then married her sister Archduchess Constance Renate of Austria.