At the age of 15, he was married to his second cousin, Princess Marie-Adélaïde of Savoy, the daughter of Victor Amadeus II, Duke of Savoy and Anne Marie d'Orléans. This match had been decided as part of the Treaty of Turin (29th August 1696), which ended Franco-Savoyard conflicts during the Nine Years' War.
The Treaty of Turin was negotiated under the influence of the Maréchal de Tessé who suggested that Marie Adelaïde be sent to France to perfect her education before marrying the French prince.
Upon her arrival in France, Louis XIV, who had come to greet her, met her in Montargis on 4 November 1696, and was quite pleased with "the Princess". As she was still a girl of 11 years, the marriage did not take place immediately and, instead, three days a week, she was a pupil at the Maison royale de Saint-Louis, the girls school Madame de Maintenon had founded in 1684 in Saint-Cyr, in the vicinity of Versailles.
On 6 December 1697, on her twelfth birthday, Princess Marie Adelaïde of Savoy was formally married to the Duke of Burgundy in the Palace of Versailles. The event took place after the signing of the Treaty of Ryswick which ended the Nine Years' War.
The new Duchess of Burgundy had a close relationship with the king and with Madame de Maintenon. Her arrival in Versailles was described "like a breath of fresh air," reviving the dull court.
The Duchess of Burgundy gave birth to her first child in 1704. The child, a short-lived boy, was given the title Duke of Brittany before his death in 1705. Marie Adélaïde bore two more children (Louis 8 January 1707 – 8 March 1712) and Louis (5 February 1710 – 10 May 1774). Her youngest son, the only child to survive beyond childhood, later became King Louis XV of France.
In early April 1711, her father-in-law Le Grand Dauphin caught smallpox and died on 14 April at the Château de Meudon. Upon the death of Le Grand Dauphin, Marie Adélaïde's husband became Dauphin of France and she Dauphine of France.
The mourning court traveled to Fontainebleau in February 1712.
At Fontainebleau, Marie Adélaïde caught a fever which escalated in measles. Having been bled and given emetics, she died in Versailles at the age of 26.
After the Dauphine's death, the royal family moved to Marly to avoid the spread of infection. It was at Marly that the Dauphin himself died six days later, having caught the measles from his wife.