He attended Mount Allison University from 1938 to 1942, where he studied under Canadian Post-Impressionists like Stanley Royle and Sarah Hart, graduating with a Bachelor of Fine Arts.

[6] His unit relieved the 82nd Airborne Division at Nijmegen, Netherlands, in mid-September 1944 during Operation Market Garden and remained there until the following February.

[5][7] Colville's painting Bodies in a Grave (1946), a scene of emaciated corpses in a Bergen-Belsen burial pit, is based on images he captured with his army-issue camera at the concentration camp.

[4] After the war, Colville returned to New Brunswick and became a faculty member with the Fine Arts Department at Mount Allison University, where he taught from 1946 to 1963.

He left teaching to devote himself to painting and print-making full-time from a studio in his home in Sackville on York Street; this building is now named Colville House.

[4] Rhoda Colville's recreational life as a swimmer, skater, dancer, singer, pianist and cyclist was featured in her husband's pieces, often set in the landscapes and waterways of Annapolis Valley.

In 2003, The Art Gallery of Nova Scotia organized an exhibition titled Alex Colville: Return curated by Tom Smart.

Upon his death in 2013, the AGO was in the process of mounting Alex Colville, the largest exhibition of the artist's work to date which opened in 2014.

Colville's work can also be found in the Art Gallery of Nova Scotia, the Cape Breton University Art Gallery in Sydney, Nova Scotia, the New Brunswick Museum, Saint John, the Museum of Modern Art in New York, the Musée National d'Art Moderne in Paris, the National Gallery of Canada in Ottawa, the Centre National d'Art et de Culture Georges Pompidou in Paris, the Wallraf-Richartz Museum in Cologne and the Kestnergesellschaft in Hanover, Germany.

Colville believed it conveyed his perception of war, as both heroism and enduring persistence among nature's elements and constant danger.

This 1954 work was inspired by two lines from the poet Roy Campbell: Horse and Train is a part of the Art Gallery of Hamilton's permanent collection; Dominion Foundries and Steel, Ltd. (Dofasco Inc) donated the painting in 1957.

Colville describes this work as an exploration of "the searching vision of the female" contrasted with the "stupid and passive" man, who she occludes.

His 1967 painting Pacific, showing a man leaning against an open door looking out to sea while a Browning Hi-Power pistol rests on a table in the foreground, inspired one of the definitive scenes in the 1995 film Heat with actor Robert De Niro.

[28] Several of Colville's paintings appear in Stanley Kubrick's 1980 film The Shining, including Woman and Terrier (1963), Horse and Train (1954), Hound in Field (1958), Dog, Boy, and St. John River (1958), and Moon and Cow (1963).