Her father, the third eldest surviving son of Empress Maria Theresa, and her mother were the founders of the House of Austria-Este.

Although Archduke Ferdinand wasn't as gifted as his eldest brother Joseph II, his rule as Governor of the Duchy of Milan made him extremely popular; he and his wife sought closeness to their subjects and owed their high esteem above all to their social commitment.

Above all, Ferdinand's thoughts were marked by his mother's dynastic way of thinking, and so he made early favorable marriage plans for his children.

Charles Theodore, Elector of Bavaria, had been married to Countess Palatine Elisabeth Auguste of Sulzbach since 1742; however, their union was not happy and only produced one son, who died in infancy.

Charles Theodore was the father of numerous illegitimate children from his relationships with Françoise Després-Verneuil and Josefa Seyffert, who hadn't any claims to the electorate.

The Palatinate-Sulzbach branch of the House of Wittelsbach was threatened with dying out after the death of the Elector if he couldn't father any legitimate descendants.

Therefore, Charles Theodore decided after the death of his wife in August 1794 to contract a second marriage with an Archduchess of the House of Habsburg-Lorraine, since they were regarded as one of the most prestigious ruling families in Europe.

Looking for a suitable Habsburg bride as the new Electress of Bavaria, Emperor Francis II selected his cousin, Archduchess Maria Leopoldina of Austria-Este, who was described as a beautiful, well-grown and educated girl.

While Archduke Ferdinand consented to the marriage between his young daughter and the aged elector, his wife Maria Beatrice had doubts.

In early January 1795 Count Maximilian von Waldburg-Zeil zu Trauchburg arrived in Milan to negotiate the marriage contract for his master the Bavarian elector.

On 12 February 1799 Charles Theodore suffered a stroke and Maria Leopoldine immediately wrote the eventual successor Duke Maximilian Joseph of Palatinate-Zweibrücken to testimony her loyalty to him: Dear nephew, at the most important moment of my life, I turn to you.

After her husband's death she quickly became known for her libertine lifestyle with permissive parties, until she became pregnant and for two years was forced to exile herself in Laibach to cover the scandal.

Maria Leopoldine recognized the high economic potential of the beautiful and fertile area and found in the person of the entrepreneur and financial expert Joseph von Utzschneider a capable and competent consultant.

However, because the groom wasn't of enough rank for an Austrian Archduchess and Bavarian Dowager Electress, Maria Leopoldine was forced to renounce her Habsburg rights for the marriage, which took place on 14 November 1804 in Munich.

During 1852–1855 under the direction of Professor Ludwig Foltz was built a crypt chapel for Maria Leopoldine, who after her death she left a fortune of 15 million florins to her two sons.