While taking refuge from the wrath of the French prime minister, Cardinal Richelieu, Gaston, Duke of Orléans, younger brother and heir presumptive of Louis XIII of France, fell in love with Marguerite.

[2] When Louis XIII was on his death bed in May 1643, he accepted his brother's plea for forgiveness, authorizing his marriage to Marguerite, whereupon the couple took their vows for the third time in July 1643 before the Archbishop of Paris at Meudon.

After the death of his mother in 1642, Gaston was bequeathed the Luxembourg Palace, which became the couple's Parisian residence under the name Palais d'Orléans once they were restored to royal favor.

Although she received a warm welcome after the death of Louis XIII, she suffered from agoraphobia and seldom visited the court where her duties were undertaken by her step-daughter, Mademoiselle, with whom she did not get along.

[3] Marguerite's husband, who had played a major part in the Fronde against his nephew the young king Louis XIV (as had her stepdaughter Anne Marie Louise d'Orléans, La Grande Mademoiselle), was exiled to his castle at Blois where he died in 1660.