On 6 March 1874, 20-year-old Lillie married 30-year-old Irish landowner Edward Langtry, a widower who had been married to Jane Francis. She was the sister of Elizabeth Francis, who had married Lillie's brother William. They held their wedding reception at The Royal Yacht Hotel in St. Helier, Jersey. He was wealthy enough to own a yacht, and Lillie insisted that he take her away from the Channel Islands. Eventually, they rented an apartment in Eaton Place, Belgravia, London before moving to 17 Norfolk Street off Park Lane.
In 1897 during her travels in the United States, Langtry became an American citizen. She divorced her husband Edward Langtry the same year in Lakeport, California. He died a few months later following an accident. A letter of condolence later written by Langtry to another widow reads in part, "I too have lost a husband, but alas! it was no great loss."