From the part of her family, the marriage was arranged with the presumption that Prince James would have a good chance to be elected king of Poland after the death of his father.

In the negotiations, it was specified that Hedwig Elisabeth would be secured a dowry of 100 000 thaler, and granted lands by the emperor in Silesia with an official residence in Oława, where the couple could settle comfortably under Imperial protection in the case Prince James would not be elected king after his father's death.

Hedwig Elisabeth was friendly received by her mother-in-law, queen Maria Kazimiera, who actively wanted to win her trust and affection and thus treated her with consideration and charm and gave her several valuable gifts.

She did, however, dislike Hedwig Elisabeth's German household retinue, as she considered them an obstacle for her daughter-in-law to acclimatize to Poland, and doubted that the Habsburg and Neuburg dynasties would support her son as future king.

Hedwig Elisabeth was described as a devoted spouse who made great efforts to work for his benefit and give him useful advise to curb unwise actions.

From the beginning, Hedwig Elisabeth was put under pressure to produce a male heir to strengthen her husband's future candidacy to the throne.

In 1704, during the imprisonment of her spouse and brother-in-law, Hedwig Elisabeth visited the Imperial court in Vienna to use her influence as a relation of the emperor in their favor and negotiate their release.