Originally known as The Daughters of the Light, the Daughters of Liberty were born out of the Age of Enlightenment, where the free expression of new ideas shaped the dignity and courage of new generations of women. They made it their mission to steward civilization in the use of those new ideas and make sure the power those ideas had was always used wisely. Through the years, they would study sorcery, science, and combat, always led by a designated Dryad. They participated in the American Revolutionary War, where they changed their name to Daughters of Liberty, and in the Underground Railroad, where they continued to earn that name.
Peggy Carter was first recruited prior to World War II by Alexa Lukin. She finished her training as the war broke out. Her first mission was to keep a close eye on Captain America, the one and only successful super soldier at the time.
During the Cold War, Lukin defected back to her home country, Russia, where she became an operative in the Winter Soldier Program, using her spellcasting to aid in the brainwashing of soldiers. As the country shifted from communism to oligarchy, so did she. She targeted Steve Rogers to get to Sharon Carter, who shot and killed Alexa's husband. This spurned a resurrected Peggy to take the role of Dryad and bring together a new team to clear Steve's name and take down Alexa.