She supported the Confederate cause by selling jewels given to her in Russia, an endeavor that helped outfit the Confederate Army unit named after her - the Lucy Holcombe Legion. Long admired for her beauty and financial support of the Confederacy, Lucy was featured on four different Confederate bills during the Civil War. Lucy became known as the “Queen of the Confederacy” after her husband was elected Governor of South Carolina in 1860. Prior to the start of the Civil War, Pickens resigned his post, and he and Lucy returned to South Carolina. The family moved oversees where Lucy became a favorite of Czar Alexander II and Czarina Maria Alexandrovna. That same year, with Lucy's support, Pickens was appointed United States ambassador to Russia. Senator Pickens was a South Carolina native, two-time widower, and the son of a former governor. He and Lucy married at Wyalucing on April 26, 1858. Lucy seems to have been well-traveled for a young woman of the mid-19th century, and on trips throughout the south she met her future husband, Senator Francis Wilkinson Pickens.
In the years that followed, the family remained staunch supporters of slavery and southern politics. Her family moved to Marshall, Texas in 1848, and their new home, Wyalucing Plantation, was built with enslaved labor between 1848–1850. She attended La Grange Female Academy and, at the age of 14 with her older sister, Anna Eliza, began attending school at the Moravian Seminary for Young Ladies in Bethlehem, Pennsylvania. Pickens was born on her family’s planation in La Grange, Tennessee. Lucy Holcombe Pickens (1832–1899), known as the “Queen of the Confederacy,” is the only woman to be featured on currency issued by a Confederate state.