The most well-known First Lady who was not married to a president is Harriet Lane, the niece of President James Buchanan, who was a lifelong bachelor. She served as the White House hostess during his presidency.
Other women have also taken on the role of First Lady without being married to the president, though they are not as well-known. This happened in cases where the president was widowed or a bachelor.
The role of First Lady traditionally goes to the president's spouse, but it has expanded to include other roles and responsibilities, such as hosting events, advocating for causes, and serving as a public representative for the president.