In October 1663, the young duke and his aunt were received in great pomp in his duchy of Joinville.

As she was a petite-fille de France, the marriage was considered a coup for the House of Guise, for the bridegroom was a mere prince étranger: Saint-Simon noted that she was a stickler for receiving the honours due her rank, even at the expense of her husband's dignity at the court of Louis XIV, inasmuch as he "was only entitled to a folding stool.

"[3] Mademoiselle de Guise carefully trained her nephew to receive Italian nobles and ambassadors who were passing through Paris, and it doubtlessly was in order to add additional luster to the couple's little court that Mlle de Guise invited Marc-Antoine Charpentier to move into an apartment at the Hôtel de Guise and compose for the young couple's chapel.

The couple had one son: The young Duke was winning the approval of Louis XIV and was given the honor of being at the King's side in military reviews.

Returning from a visit to the court of Charles II, king of England, he fell ill with smallpox on 18 July 1671, and died twelve days later.