She fell in love with the flamboyant and charismatic Joachim Murat, one of her brother's senior cavalry commanders, and they married on 20 January 1800.

Caroline became Grand Duchess of Berg and Cleves on 15 March 1806 and Queen consort of Naples on 1 August 1808, when her husband was appointed to the equivalent positions by her brother.

As queen, Caroline renovated the royal residences in Naples, had new gardens planned, encouraged the growing interest in furniture of classical design, patronized the silk and cotton industry and French artists in Naples, showed an interest in the archaeological discoveries of Pompeii and founded a school for girls.

She was described as intensely jealous of her sister-in-law Joséphine and her children, reportedly because she felt Napoleon favored them over his Bonaparte relatives.

It was reportedly Caroline who arranged for Napoleon to take a mistress, Éléonore Denuelle, who duly gave birth to his first illegitimate child.

[3] This had the desired effect of establishing that Joséphine was infertile, as Napoleon showed he was clearly capable of siring children, which eventually resulted in his divorce from Josephine and remarriage.