[1] A year after succeeding to the throne, Leopold was married on 17 April 1852 in Rudolstadt to Princess Elisabeth of Schwarzburg-Rudolstadt (1833–1896) the daughter of Prince Albert of Schwarzburg-Rudolstadt and Princess Augusta of Solms-Braunfels.

At his ascension, the principality was a member of the German Confederation, and Leopold supported Prussia during the Austro-Prussian War of 1866.

Prince Leopold was one of the main promoters of the creation of the Hermann monument in the Teutoburg Forest which was opened by the German Emperor William I in the summer of 1875.

As Leopold was childless, his brother Woldemar succeeded him as Prince of Lippe.

The composer Johannes Brahms was a member of the prince's household between 1857 and 1859 as a conductor and music teacher to his sister Princess Friederike.