On 25 May 1685, at the age of eleven, Louise Françoise was married to Louis de Bourbon, Duke of Bourbon, a distant sixteen-year-old cousin of her father, the King Louis XIV of France.
Louis XIV gave his daughter a large dowry of one million livres upon her marriage.
In an age where dynastic considerations played a major role, eyebrows at court were raised at a marriage between a full-blooded prince du sang and a royal bastard. The head of the House of Condé, le Grand Condé, however, acquiesced to the socially inferior match in the hope of gaining favour with the bride's father, Louis XIV.
The seventeen-year-old duc de Bourbon was known at court as Monsieur le Duc. After the marriage, his wife assumed the style of Madame la Duchesse. Like his father, who became Prince of Condé in 1687, Louis de Bourbon led a typical, unremarkable life.
Some time after her marriage in 1686, while the court was in residence at the Palace of Fontainebleau, Louise Françoise contracted smallpox. While her then seventeen-year-old husband did not help nurse her back to health, her mother and grandfather-in-law, Le Grand Condé, did. Louise Françoise recovered, but Le Grand Condé died the following November after having caught her illness. Louise Françoise and her husband eventually had nine children, all of whom survived into adulthood.