Dolgoff was born in the shtetl of Ostrovno in Vitebsk Governorate, Russian Empire (in present-day Beshankovichy Raion, Belarus), moving as a child to New York City in 1905 or 1906, where he lived in the Bronx and in Manhattan's Lower East Side where he died. His father was a house painter, and Dolgoff began house painting at the age of 11, a profession he remained in his entire life.
After being expelled from the Young People's Socialist League, Sam joined the Industrial Workers of the World in the 1922 and remained an active member his entire life, playing an active role in the anarchist movement for much of the century. He was a co-founder of the Libertarian Labor Review magazine, which was later renamed Anarcho-Syndicalist Review to avoid confusion with America's Libertarian Party.
Dolgoff was a member of the Chicago Free Society Group in the 1920s, Vanguard Group member and editor of its publication Vanguard: A Journal of Libertarian Communism in the 1930s, and co-founded the Libertarian League in New York in 1954. He wrote articles for anarchist magazines as well as books as the editor of highly-acclaimed anthologies, some of which are listed below. He was active in many causes, and attended groups like New York's Libertarian Book Club regularly.
Dolgoff, and his wife Esther, served as a link to anarchism's past to young anarchists of the 1960s and 1970s living in New York. He focused upon anarchism's (specifically anarcho-syndicalism's) roots in workers' movements and served as a moderating counterbalance to the punk-era anarchists who tended towards 'monkeywrenching' and confrontations with the police. Although Dolgoff was friends with Murray Bookchin, a notable anarchist theorist of the period, he was opposed to Bookchin's theory of Social Ecology, rooted as he was in the classical anarchist traditions of Mikhail Bakunin and Peter Kropotkin.
- Ethics and American Unionism (1958)
- The Labor Party Illusion (1961)
- Bakunin on Anarchy (1971; revised 1980)
- The Anarchist Collectives: Workers' Self-Management in the Spanish Revolution, 1936-1939 (1974)
- The Cuban Revolution: A Critical Perspective (1974)
- A Critique of Marxism (1983)
- "Modern Technology and Anarchism" (1986)
- Fragments: A Memoir (1986, ISBN 0-946222-04-5).
- Porton, p.40
- Avrich, p.419
- Avrich, ibid.
- Avrich, p.420
- Kayton, p.155
- Greeman, p.13
- Sam Dolgoff, 88, Dies; Organizer for I.W.W., New York Times, October 26, 1990. 
- Avrich, Paul. Anarchist Voices: An Oral History of Anarchism in America, AK Press,
- Greeman, Richard. Dangerous Shortcuts and Vegetarian Sharks, ISBN 1-4303-2307-8.
- Kayton, Bruce. Radical Walking Tours of New York City, Seven Stories Press, 2003, ISBN 1-58322-554-4.
- Porton, Richard. Film and the Anarchist Imagination, Verso, 1999, ISBN 1-85984-702-1.
- An obituary and short biography of Sam Dolgoff on libcom.org