Born in Chillicothe, Ohio, the daughter of James Webb, a doctor, and Maria Cook-Webb, Lucy was descended from seven veterans of the American Revolution. Her father died when she was a child. With her mother, she moved to Delaware, Ohio where in 1847 she met Rutherford B. Hayes. Later that year, she enrolled at Wesleyan Women’s College, class of 1850 (which later merged with Ohio Wesleyan University); she was the first first lady to have graduated from college and was a member of Kappa Kappa Gamma sorority. Hayes was by this time practicing law in Cincinnati, and the two began dating seriously. He proposed in June 1851.

Rutherford Hayes, aged 30, married Lucy Webb, aged 21, on December 30, 1852, at the home of the bride’s mother in Cincinnati, Ohio. After the wedding, performed by Dr. L.D. McCabe of Delaware, the couple honeymooned at the home of the groom’s sister and brother-in-law in Columbus, Ohio.  A vigorous opponent of slavery, Hayes contributed to her husband’s decision to abandon the Whigs for the antislavery Republican Party. During the American Civil War, she visited Hayes often in the field. While her husband was governor of Ohio, she helped establish the state Home for Soldiers’ Orphans at Xenia.

As First Lady, Hayes brought her zeal to the White House and supported her husband’s ban of alcoholic beverages at state functions, excepting only the reception for Grand Duke Alexei Alexandrovich of Russia in 1877, at which wine was served. The Women’s Christian Temperance Union hailed her policy and in gratitude commissioned a full-length portrait of her, which now hangs in the White House. She also instituted the custom of conducting an Easter egg roll on the White House lawn. A devout Methodist, she joined the president in saying prayers after breakfast and conducting group hymn sings with the cabinet and congressmen on Sunday evenings.  The social highlight of the Hayes’s years was their twenty-fifth wedding anniversary celebration, at which the President and the First Lady repeated their vows at a White House ceremony before many of the same guests who had attended the original nuptials in Cincinnati.

In 1881 she retired with the President to Spiegel Grove in Fremont, Ohio. She died of a stroke on June 25, 1889, and was buried at Spiegel Grove. Upon her death, flags across the United States were lowered to half-staff.