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She was born Ann Ward in Holborn, London, England, Kingdom of Great Britain. She married William Radcliffe, an editor for the English Chronicle, at Bath in 1788. The couple were childless. To amuse herself, she began to write fiction, which her husband encouraged.
She published The Castles of Athlin and Dunbayne in 1789. It set the tone for the majority of her work, which tended to involve innocent, but heroic young women who find themselves in gloomy, mysterious castles ruled by even more mysterious barons with dark pasts.
Her works were extremely popular among the upper class and the growing middle class, especially among young women. Her works included The Sicilian Romance (1790), The Romance of the Forest (1791), The Mysteries of Udolpho (1794), and The Italian (1796).
The success of The Romance of the Forest established Radcliffe as the leading exponent of the historical Gothic romance. Her later novels met with even greater attention, and produced many imitators, and famously, Jane Austen's burlesque of The Mysteries of Udolpho in Northanger Abbey, as well as influencing the works of Sir Walter Scott and Mary Wollstonecraft (Writer of Philosophy).
Stylistically, Radcliffe was noted for her vivid descriptions of exotic locales, though in reality the author had rarely or never visited the actual locations.
She died on February 7, 1823 from respiratory problems probably caused by pneumonia.
Her own view of her work and time appeared in 1826 under the title "On the Supernatural in Poetry", by the late Mrs Ann Radcliffe.