[5] Although only two years younger, Polyxena was a niece of Charles Emanuel's first wife,[5] and belonged to the Hesse-Rotenburg line, which was the only Roman Catholic branch (since 1652) of the reigning House of Hesse.

[9] Her stepson Victor Amadeus, heir after his father and grandfather to the Sardinian crown, died at the age of two, a year after Polyxena's marriage and before she had a child of her own.

Nonetheless, she is said to have had a close relationship with her mother-in-law, Anne Marie d'Orléans, and the two frequented the Villa della Regina outside the capital, where the latter died in 1728.

[11] In an 1869 history of the House of Savoy, Francesco Predari wrote that despite the fact Polyxena was praised for goodness of character and beautiful virtues, her father-in-law advised her to take care to maintain separate quarters from her husband for prudence's sake.

Two years after her death, her widower married Princess Elisabeth Therese of Lorraine,[13] sister of the future Francis I, Holy Roman Emperor.