Joséphine Caroline married her maternal first cousin Prince Karl Anton of Hohenzollern-Sigmaringen on 28 May 1894 in Brussels.

During World War I, she made her home a military hospital for wounded soldiers while her husband served as a Prussian lieutenant general.

In 1935, Joséphine Caroline entered a Benedictine convent in Namur, taking the name of Sister Marie-Josephine, and remained a nun for the rest of her life.

She is buried in the Couvent des Soeurs de Notre-Dame (Convent of the Sisters of Our Lady) in Namur.

On 28 May 1894 in Brussels, she married her maternal first cousin Prince Karl Anton of Hohenzollern-Sigmaringen, later simply of Hohenzollern (Sigmaringen, 1 September 1868 – Namedy, 21 February 1919), third son of Leopold, Prince of Hohenzollern-Sigmaringen, later simply of Hohenzollern and Infanta Antónia of Portugal.