Caroline was considered as a bride for Louis Antoine Henri de Bourbon, Duke of Enghien, but the fear of attracting opposition from France made her family hesitate.

On 9 March 1797, in Karlsruhe, she became the second spouse of Maximilian, Duke of Palatine Zweibrücken, who two years later would inherit the Electorate of Bavaria.

She was described as a very dignified consort and hostess of the Bavarian court and raised her daughters to have a strong sense of duty.

The Protestant clergy were halted at the church door and not allowed to proceed inside for the service, so Ludwig Friedrich Schmidt gave the funeral sermon there.

This treatment of his beloved stepmother permanently softened the attitude of Caroline's stepson Ludwig I of Bavaria, who up until that time had been a strong opponent of Protestantism despite his marriage to the Protestant princess Therese of Saxe-Hildburghausen.