The second of three children to reach adulthood, her older brother Charles Frederick succeeded their father as Grand Duke in 1828.

One of Caroline's nieces was Empress Augusta of Germany, wife of William I, German Emperor.

The Hereditary Grand Duke had lost his first wife Elena Pavlovna of Russia in September 1804 having died of influenza.

[citation needed] After the birth of her youngest child, Prince Magnus, her health never recovered and she died aged 29 at the Schloss Ludwigslust.

In her deathbed, she suggested her husband remarry to her cousin Auguste Fredericka, daughter of Frederick V of Hesse-Homburg; they married in April 1818.