The son of Richard Caton Woodville, Sr., who was also a talented artist, Woodville studied at the Düsseldorf School of painting under the Prussian military artist Wilhelm Camphausen, and then Eduard von Gebhardt, before briefly studying in Russia and then Paris under Jean-Léon Gérôme. Woodville spent most of his career working for the Illustrated London News, where he quickly developed a reputation as a talented reporter and writer, but was also published in Cornhill Magazine, Strand Magazine, and The Tatler.
Woodville is best known for his battle scenes, the earliest of which were of the Russo-Turkish War (1877–1878) where he was sent by the Illustrated London News. He also covered the 1882 Anglo-Egyptian War, where he made numerous sketches in December 1882.
In 1879, Woodville's painting Before Leuthen, 3 Dec 1757 was exhibited in the Royal Academy. It proved popular, and afterwards he began to regularly be exhibited in Burlington House, where 21 of his battle paintings were eventually shown. Few battles or wars that Great Britain fought during his life were not touched upon by him, including the Second Boer War, and World War I.
During his lifetime, Woodville enjoyed great popularity. He wrote as well as painted, and was often the subject of magazine and journal articles. He had a deep passion for the British Army and had even joined the Berkshire Yeomanry in 1879, staying with them until 1914 when he joined the National Reserve as a Captain.
On 17 August 1927, Woodville was found shot at his studio at St John's Wood; a revolver was also found. An inquest determined that he was of unsound mind when he committed suicide. Caton Woodville died effectively destitute and his grave (No 10112 in the old section of St Mary's Catholic Cemetery in Harrow Road adjacent to Kensal Green cemetery), was not marked at the time of his death.