The 43-year-old "Peep Show" actor will star in the new TV series written by former "Simpsons" writer Julie Thacker Scully and directed by Ben Taylor.
Webb plays divorcee Jack, whose search for a fresh start with new love Sara (played by Melanie Lynskey) is scuppered by his ex-wife Hillary (Victoria Hamilton), reported Digital Spy.
"Our Ex Wife" is one of five new sitcoms announced by the BBC as part of its 'Landmark Comedy' season.
The new comedies will sit alongside revivals of classic sitcoms including "Are You Being Served?", "Porridge", "Keeping up Appearances" and "Goodnight Sweetheart".
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