The marriage to Napoleon, in 1811, linked her father's Austrian Empire with Napoleon's France. The empress had a son, Napoleon Francis Joseph Charles Bonaparte, styled King of Rome and later Duke of Reichstadt. After Napoleon's abdication Marie Louise and her son fled Paris to Blois then to Vienna where she remained until granted the duchies of Parma, Plaisance, and Guastalla by her family.
In 1821, four months after Napoleon's death, she married, morganatically, her lover, Adam-Adalbert, Count and Lord of Neipperg (1775-1829). The couple had two children out of wedlock: Albertine, Countess of Montenuovo (1817-1867, married Luigi, Count di Fontanellato) and Wilhelm Albrecht, Count of Montenuovo, later created Prince of Montenuovo (1819-1895, married Countess Juliana Batthyány von Némét-Ujvár). Marie-Louise and Neipperg also had a second daughter, Mathilde, Countess of Montenuovo, in 1822. In 1834 Marie-Louise married, morganatically, her grand chamberlain, Charles-René, Count of Bombelles (1785-1856).