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A limited-edition range of 11 clothing items will go on sale in 60 Primark stores from February 19.
Both brands revealed the new partnership, which includes a new 130-seat "Tasty by Greggs" cafe in Primark Birmingham opening on February 12, in a video shared across their social media channels.
The announcement follows shoppers spotting fashion mannequins at a number of Primark stores holding Greggs sausage rolls and steak bakes in window displays.
Greggs and Primark will open an appointment-only boutique on London's Dean Street in Soho on February 17-18, allowing eager fans a chance to select items for free ahead of the collection going on general sale.
The appointment system will open for booking via a link that will be shared on both Greggs and Primark Instagram and Facebook pages at 10am on Thursday.
Greggs business development director Raymond Reynolds said: "Greggs clothing is something our customers have continually asked for, so it's great that together with Primark we can now make our first official range available across the UK - so that fans can quite literally show their love for Greggs on their sleeves.
"Our 'Tasty by Greggs' cafe will be the first of its kind, and will offer an exciting Greggs experience."
Tim Kelly, director of new business development at Primark, said: "We're thrilled to have teamed up with Greggs to bring the Tasty Cafe to our Birmingham store and give fans of the brand the chance to get their hands on the limited-edition clothing range."