Privately educated, Whymper entered his father's wood engraving business and ultimately succeeded as head of it. He was sent to Switzerland in 1860 to make sketches for a book on the Alps and became a mountaineer thereafter. In the western Alps he climbed Mont Pelvoux (1861) and Les Écrins (1864). On his eighth attempt to scale the Matterhorn, on July 14, 1865, Whymper made the ascent by the Swiss ridge. On the descent, one member of his party slipped and pulled down three more—all four fell to their deaths. The rope broke, saving Whymper and two guides. One of the best known of all mountaineering accidents, this event is recorded in Whymper's Scrambles Amongst the Alps (1871; condensed as Ascent of the Matterhorn, 1879), which is illustrated with his own engravings.

In 1867 and 1872 Whymper visited Greenland with the intention of crossing its ice cap, but he became convinced that the undertaking would prove too costly for him. In Ecuador (1880) he twice ascended Chimborazo, and he spent a night on the summit of Cotopaxi (19,347 feet 【5,897 metres】), the world's highest continuously active volcano. He published Travels Amongst the Great Andes of Ecuador (1892), which contained much valuable information for geographers, geologists, and mountaineers. He also compiled two handbooks on the climbing of Chamonix (1896) and Zermatt (1897; both reprinted 1974). Whymper's last journeys were in the Canadian Rockies (1901–05).