Leopoldine's oldest sister, Eleonore Magdalene, became the Holy Roman Empress in 1676, as the third wife of Leopold I; this helped her numerous siblings to secure brilliant careers and marriages.

After her father's death in 1690, Leopoldine was under the legal guardianship of her older brother Johann Wilhelm, who also supervised her education.

In addition to language, religion, and handicrafts, the young princess learned music from the Kapellmeister Sebastiano Moratelli.

It was there that, thanks to the care and affection of her sister-in-law, Anna Maria Luisa de' Medici, her condition improved.

In March 1693, she was formally betrothed to Maximilian II Emanuel, Elector of Bavaria,[1] whose first wife, Maria Antonia of Austria, had died in December 1692.