She was born to Ernst Frederick, Duke of Saxe-Coburg-Saalfeld and Sophia Antonia of Brunswick-Wolfenbüttel in Coburg. She was an aunt to Leopold I of Belgium and Marie Luise Victoria, the mother of Queen Victoria. Her father was largely indebted by 1773 thus her family wanted to find Caroline a good (i.e. wealthy and high-ranking) husband. After much searching, her parents decided she should marry Prince Ambroos of Brunant, a young boy who was related to Polish and German royalty. Caroline was engaged to Prince Ambroos of Brunant at the age of 15 (in 1777) but they were only married in 1781.
It was generally believed that their marriage was purely for political purposes, since Caroline came from an important family, but many love letters have been found written between the two, meaning likely that they truly fell in love. Since Ambroos was still off studying in England, Caroline remained in Brunant since she did not want to move there. Caroline gave birth to twin daughters when Ambroos was away. The couple were re-united in 1783 when he finished studying. Caroline and Ambroos would have the following nine children:
- Princess Cristina Maria (1782-1805), married to Ernest Augustus I of Hanover.
- Princess Augustina (1782-1833)
- Princess Helena (1784-1821)
- Princess Victoria (1786-1838), married to David James Carrington and had issue.
- Cristian I (1787-1859), married to Maria Francesca of Naples and Sicily and had issue.
- Princess Louisa (1790-1884)
- Princess Maria (1792-1863)
- Prince Johan Alexander (1794-1855)
- Princess Juliana (1795-1870), married to Alexander von Krupski and had issue.
Caroline was left a widow when Ambroos died in 1823. She died in 1828 and was outlived by seven of her children.