Munster thought they had the game won when Paul O'Connell marked his return from injury with a try that handed his team a 22-11 lead after an hour. But Jamie Roberts stormed over to haul Cardiff back into contention before delivering the scoring pass for Selley to steal a sensational late win.
The victory lifts the Cardiff Blues up to second in the Magners League and strikes a minor psychological blow for Wales over Ireland ahead of next week's Triple Crown clash.
However, both national coaches will have been satisfied following the performances of Wales wing Roberts and Ireland lock O'Connell who are both set to feature in Dublin.
It was a remarkable turnaround after Munster took the lead inside 48 seconds. Their pack stole possession back from the kick off, Alan Quinlan pulled the Blues defence in one direction before Warwick sent Munster the other for Payne to score.
The Blues defence were caught short and for Payne who had time to let the ball settle before pouncing to score. It was simple stuff, yet ever so effective. Warwick guided his conversion in off the post from close to the left-hand touchline for a seven-point lead until Roberts fed off Gareth Thomas to lead the recovery.
The Wales wing raced onto Thomas's off-load and smashed through Munster's tackles to set up Blair's first penalty before Rhys Thomas dived over on 20 minutes.
Jamie Robinson split the Irish defence, Xavier Rush kept the Blues moving forward with a trademark charge before delivering the scoring pass.
Yet despite the turnaround, the Blues trailed 10-8 at the break as Blair and Rhys Jones missed kicks into the stiff wind and scrum half Richie Rees fluffed a two-on-one advantage, after Warwick's penalty.
Munster made Cardiff pay with two tries in the space of 12 minutes in the second half. Prop Buckley stormed over from close range on 46 minutes before O'Connell followed after Anthony Foley was stopped short.
A 22-11 lead should have proved enough but Roberts powered over from Thomas's break to set up a thrilling climax to a pulsating game.
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