Tointon, who played Eliza Doolittle in Pygmalion alongside Rupert Everett earlier this year, will be joined in Absent Friends by Reece Shearsmith, Elizabeth Berrington, Katherine Parkinson, David Armand and Steffan Rhodri.
The production, which will open on 9 February (previews from 26 January), is being produced by Sonia Friedman Productions and Bob Bartner.
Ayckbourn's 1974 play centres on a couple who organise a gathering to comfort their friend Colin, whose fiancee has recently drowned. The problem is that the friends are far more miserable than the man they have gathered to help.
Former EastEnders star Tointon will play the cruel-minded Evelyn, who has had an affair with her husband's married friend. Colin will be played by League of Gentlemen star Reece Shearsmith, who was recently seen in Betty Blue Eyes.
Katherine Parkinson, who plays Diana, is best known for playing Jen in Channel 4's The IT Crowd and recently appeared in Ayckbourn’s Season’s Greetings at the National Theatre.
The cast is completed by Elizabeth Berrington (Abigail's Party) as Marge, Steffan Rhodri (The Kitchen Sink, Gavin and Stacey) as Paul and David Armand (TV's Sorry I’ve Got No Head and Fast and Loose) as John.
Currently at the Harold Pinter (formerly the Comedy), Ariel Dorfman's Death and the Maiden, which is also directed by Herrin and stars Thandie Newton in her stage debut, continues until 31 December.