Hedwig was a daughter of the Duke and Count Palatine Christian August of Sulzbach (1622–1708) from his marriage to Countess Amalie of Nassau-Siegen (1613–1669), daughter of Count John VII of Nassau-Siegen.

She was married on 3 June 1665 per cura in the court chapel of Sulzbach to Archduke Sigismund Francis of Austria-Tyrol (1630–1665), who after his brother's unexpected death had resigned from his ecclesiastical positions in order to marry.

Hedwig's second marriage, in Sulzbach on 9 April 1668, was with Duke Julius Francis of Saxe-Lauenburg (1641–1689).

Her father had a memorial stone erected in the Sulzbach parish church to commemorate the event.

Hedwig died in 1681 and was buried in the White Castle at Ostrov (German: Schlackenwerth).