Hedwig married on 7 February 1619 in Wolfenbüttel to Ulrich, Duke of Pomerania (1589–1622), Bishop of Cammin.

Among the Duchess's entourage was Christopher of Hoym, who would later become Marshal of the last Duke of Pomerania, Bogislaw XIV.

Her complaints to her cousins King Christian IV of Denmark and Queen Christina of Sweden were unsuccessful.

In 1631, she appointed Gregor Lagus, who was Rector of the Latin school at Kołobrzeg as provost in Szczecinek, despite opposition from Duke Bogislaw XIV.

[1][2] In 1642, Hedwig was wounded during a raid by the Polish noblemen Bartholomew Tarno from Strączno, Pipilowski from Czarnków and voivode Melchior Weiher of Chełmno.