Born in London, she is the daughter of property consultant Ian Strathearn Gordon, and magistrate Nicola Mary Gordon. She studied at RADA in the same year as Jane Horrocks, where the two became best friends. After college they shared a flat in Bayswater and celebrated their joint 30th birthday party at the Groucho Club.
Gordon separated from her husband, Tim Laurence in 2011. Together they still run the UK branch of the Hoffman Institute, which presents a psychological programme founded by Bob Hoffman in 1967. They have two sons.
In 2013, Serena Gordon married Adam Douglas who is an antiquarian books dealer, with two children Raphael and Brigit Douglas, in Arundel, West Sussex.