The 'Maggie May' hitmaker is expected to welcome his former Faces bandmate onto the stage at London's Hyde Park towards the end of his headline set at Hard Rock Calling tomorrow to play some of their old hits.
A source told the Daily Star newspaper: "Rod's back catalogue is huge but it will be a really special moment for his fans when Ronnie comes on."
Meanwhile, last night's headline band, The Killers have hinted they could debut some of their long-awaited new material alongside classic hits including' Bones', 'When You Were Young' and 'Mr. Brightside'.
Speaking after their intimate warm-up show at London's Scala earlier this week, drummer Ronnie Vannucci said: "Hard Rock Calling is a f***ing great show - I love that show. We're having our cake and eating it too.
"These intimate gigs are sweaty, where everyone's like five feet away and you can see the whites of their eyes. You really connect on a more immediate and personal level.
"But when you have 70,000 people, your gestures have to be bigger. It's so important about being able to address a group, making a group feel as one.
"And that's something that's a learned thing, we're still trying to get our heads around it. As for us playing new songs, we might have a surprise for you."
Joining The Killers and Rod as headliners of this year's Hard Rock Calling, Bon Jovi will top the bill tonight.