The 35-year-old actress – who created and starred in the tragicomedy show Fleabag – has signed on to appear in the new TV series for Amazon Studios.
Jennifer Salke, the Amazon Studios chief, said: “Talk about the dream team! Donald and Phoebe are two of the most talented creators and performers in the world.
“It’s truly a dream for us, as it will be for our global audience, to have these two forces of nature collaborating as a powerhouse creative team. Mr and Mrs Smith is an iconic property, and we can’t wait to see how Donald, Phoebe and Francesca [Sloane, the showrunner] make it their own.
“We’re thrilled to be working with them, and with such great partners at New Regency.”
The Mr & Mrs Smith movie starring Brad Pitt and Angelina Jolie was released back in 2005.
The film saw the Hollywood duo play a married couple who worked as assassins belonging to competing agencies.
Phoebe previously worked alongside Donald, 37, on Solo: A Star Wars Story, and she’s also helped to write the new James Bond film, No Time to Die.
Speaking about her Bond experience, she previously said: “The wonderful thing is … you have these incredible conversations about this iconic character who you’ve grown up with.
“Then when you’re on board, it’s like every other job because everyone is just making a story, making a thing work.
“And you’re just suddenly in a room again with post-its on the wall, and then you’ll go to the loo and you’ll see a set being built outside for some extraordinary thing and you’re like, ‘Oh yes, this is different, this is different from Fleabag.'”