She also had two half-siblings from her father's previous marriage to Catherine Pavlovna of Russia: Marie and Sophie, the future Queen consort of the Netherlands.

The marriage was meant to strengthen ties between the main branch of the Württemberg family and the next possible heir to the throne.

As the marriage seemingly predicted, they had one son, who would eventually succeed her childless brother Charles as King of Württemberg:[citation needed] Frederick died in 1870.

In the 1880s, Catherine was described as a "portly, austere old widowed Princess...who had a red, mannish face, and habitually dressed in purple and mauve".

In this location, she was a neighbor of her relatives, the Tecks, who included the future Queen Mary of the United Kingdom.