After the death of her father, she married secretly without the knowledge of her mother on 14 July 1672 to Duke Frederick von Schleswig-Holstein-Sonderburg-Wiesenburg (b.
Her godfather was a senior member of the family, Duke George Rudolf of Liegnitz, but he was seriously ill at the time of her birth.
He died thirteen days later on 14 January, so he was replaced during the ceremony by her paternal uncle, Louis IV of Legnica.
However, in 1664, after the death of his only surviving brother, George III, Karolina's father united the whole Duchy of Legnica-Brzeg under his rule.
Duke Christian died on 28 February 1672 and was succeeded by his only surviving son, George William, who was placed under the regency of his mother.
On 21 November 1675, Karolina's brother George William, the last Piast ruler of Legnica-Brzeg, died underage and without male heirs.
Her heart was placed in a silver urn in the local church of St. Klara (in the chapel of St. Hedwig), and her body was buried in the monastery of Trzebnica.