X-Men: First Class's James McAvoy and Game of Thrones' Natalie Dormer will lead the cast on the forthcoming BBC Radio 4 production.
Benedict Cumberbatch, Sophie Okenodo, Anthony Head, Bernard Cribbins and horror legend Christopher Lee will also lend their voices to the adaptation.
Gaiman posted the announcement and cast list, alongside a photograph of members of the production, on his blog.
"The adaptation is by Dirk Maggs, who did the last three Hitchhiker's Guide Radio adaptations," he wrote.
"He's co-directing it with producer Heather Larmour, who is the one who went off and made this happen after a small enthusiastic chat in a London coffee shop much earlier this year - the kind of conversation that you have that normally just leaves you feeling happy, but doesn't actually turn into anything real. This time it did."
Neverwhere originally aired as a television show on BBC Two in 1996. Gaiman later published the story as a novel, which was also adapted into a comic series by Mike Carey and Glenn Fabry in 2005.
The radio play will debut in early 2013.