McAvoy is from Scotstoun, Glasgow. He attended St Thomas Aquinas Secondary in Jordanhill, Glasgow. McAvoy graduated from the Royal Scottish Academy of Music and Drama in 2000. He is married to his Shameless co-star, Anne-Marie Duff.

McAvoy's first roles were in David Hayman's The Near Room in 1995 and then as Anthony Balfour in Pat Barker's Regeneration in 1997. McAvoy got his first big international break playing the role of Leto Atreides II in the Sci Fi Channel miniseries Children of Dune (adapted from Frank Herbert’s novels) which aired in 2003. In 2004 he starred as Steve McBride in another Abbott-written drama series, Shameless on Channel 4, for which he was nominated for the British Comedy Award for Best TV Newcomer. In 2005, he played Ben in the Royal Court Theatre's production Breathing Corpses,as well as the role of Mr. Tumnus, the Faun in Disney and Walden Media's The Chronicles of Narnia: The Lion, the Witch and the Wardrobe. He also starred in Wimbledon as Carl Colt. He also starred as Macbeth in Shakespeare Retold.

In 2006 he starred alongside Forest Whitaker in an adaptation of Giles Foden’s novel The Last King of Scotland based on the (factual) events of the brutal Ugandan dictator Idi Amin’s regime as seen by his (fictional) personal physician during the 1970s. He took the lead, Brian Jackson, in Starter for Ten (the adaptation of the David Nicholls novel of the same name).

McAvoy has roles in two films for 2007 - Becoming Jane and Atonement. McAvoy is currently at work on the film adaptation of Wanted. He is rumoured to be in the running to play Montgomery Scott in the upcoming eleventh Star Trek film, and the Channel 4 mini series "The Devil's Whore".

McAvoy won the new Mary Selway/Orange Rising Star Award at the 2006 BAFTA Awards.

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