Dorothea (Dolley) Payne Todd was born in Guilford County, North Carolina. Her parents, John and Mary Coles Payne, were devout Quakers. Her father had tried farming in Virginia and North Carolina, and not having much success, moved to Philadelphia and went into the business of manufacturing starch. Her father was again unsuccessful and was near bankruptcy when a lawyer, named John Todd, came into the business and turned it around. Todd also gave Mrs. Payne a job as a keeper of a boarding house. In admiration and gratitude, Dolley married John Todd on January 7, 1790. In 1793, Philadelphia had fallen victim to the yellow-fever epidemic, and Dolley lost her husband as well as her youngest of two children. Dolley had come to know Senator Aaron Burr, as he was a boarder at her mother's boarding house. It was Burr who introduced Dolley to James Madison. They became engaged in the summer of 1794, and were married September 15, 1794, at Harewood, the Virginia Plantation of one of George Washington's nephews, who was the husband of one of Dolley's sisters.

In 1809 Dolley became the mistress of the White House. She had always given lively parties and receptions, organizing the first White House wedding for her sister Lucy, who married a Supreme Court Justice. She was also responsible for finishing and decorating the East Room and the Oval Room. In 1814 when the British burned and captured Washington, Dolley, having been deserted by the guards posted there for her protection, became a heroine. It was she who packed up the valuables and papers, as well as the famous painting of George Washington by Gilbert Stuart, placed them in wagons and sent them to secure locations, getting out just in time herself. She spent the next three days in Virginia, trying to find her husband, and finally returning to Washington on foot, to find the charred capital.

After Madison's two terms as President, he and Dolley retired to their plantation, Montpelier, in Virginia. They never once visited Washington. Upon her husband's death, her financial situation crumbled, causing her to lose Montpelier and almost all her belongings. She then retired to a little house she owned in Washington, living there in poverty until her death on July 12, 1849. Throughout this difficult time she never lost her dignity.