Catherine was the second daughter of François de Clèves, Duke of Nevers, and Marguerite de Bourbon, elder sister of Antoine de Bourbon. She was the first cousin of Henry of Navarre, sister-in-law of Henri de Bourbon, Prince of Condé, and great aunt of Ludwika Maria Gonzaga, Queen of Poland. At the age of twelve, Catherine married Antoine de Croÿ, :fr:Liste_des_comtes_de_Porcien#Prince_de_Porcien|Prince de Porcien, who died seven years later. After the conventional three years of mourning, on 4 October 1570, she married Henri de Lorraine, Duke of Guise, who was two years her junior. They had fourteen children, including Charles, Duke of Guise and Louis III, Cardinal of Guise. She had a widely publicised affair with a young nobleman, Saint-Mégrin, who was killed by her husband. The event is dramatised in the Alexandre Dumas play Henri III et sa cour. Henry of Guise was the leader of the fervently Catholic faction in the French Wars of Religion. From 1584, the conflict among factions led by Henry of Guise, Henry of Navarre, and Henry III of France was known as the War of the Three Henrys. In 1588, Henry of Guise was assassinated on the orders of King Henry III. Catherine never forgave Henry III of France for his part in the assassination of her husband. She took a keen interest in the intrigues of the Catholic League and encouraged Henry's assassination in 1589. At the conclusion of the War of the Three Henrys she was mindful of the interests of her large family and supported her son Charles as a candidate for the French throne. Catherine's reconciliation with her cousin, Henry IV, was not effected until his conversion to Catholicism. She immediately moved to Paris and obtained a very honorable position in the retinue of his wife, Marie de' Medici. In 1613, Catherine interceded for her son, François Alexandre, who had killed the Baron of Luz in a duel, asking for his banishment instead of execution for murder. The Guises continued to support the Queen throughout the regency, and Catherine followed Marie into exile in Blois after Louis XIII assumed the reins of government in 1619. After returning to the Louvre, the Dowager Duchess - anxious to promote the interests of the House of Guise - resumed plotting against Cardinal Richelieu. The death of her youngest daughter, the princesse de Conti, proved a blow to her spirits. She retired to her château d'Eu, where she died aged 85. She was buried at the château next to her husband's ornate tomb.
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She married on October 4, 1570 in Paris to Henri de Lorraine, Duke of Guise, by whom she had fourteen children:
