Rhodes grew up in Devon, and graduated in Humanities from the University of Glamorgan (now the University of South Wales) in 1994, returning in 1997 to complete an MA in Creative Writing. Don't Tell Me the Truth About Love was written at this time. He has held a variety of jobs, including stockroom assistant for Waterstone's, barman in his parents' pub, and a Teacher in Ho Chi Minh City. He has also worked on a fruit and vegetable farm and is still employed as a postman.

Rhodes was included on Granta's Best of Young British Novelists list in 2003, to his own bemusement and frustration, partly because of Granta's selection methods ("It's one thing to judge a Writer by stuff they've written, but to judge them on stuff they're going to write is lunacy") but also because some of the others on the list failed to respond to his request to sign a joint statement protesting the Iraq war.

As of December 2015, Rhodes's most recent novel is When the Professor Got Stuck in the Snow, a "rural farce" about a visit to an obscure English village by a fictional Richard Dawkins. Rhodes initially self-published the novel in February 2014 stating on his blog that he wanted to get the book out faster than conventional publishing allows, although it soon became apparent that formal publishers were loath to publish the novel for fear of legal action from Professor Richard Dawkins. Rhodes appealed repeatedly to Dawkins, a defender of satire and free speech, for permission to "publish and be damned" but received no response. The novel was published by Aardvark Bureau in October 2015.