Nineteen points from the boot of captain Greig Laidlaw combined with tries from Matt Scott and Steve Lawrie proved sufficient to see off a lacklustre visiting side, whose sole try came from replacement Danny Barnes, the rest of their points added by fly-half Ian Keatley.
The reigning league champions, who had held a 100% record until this encounter, made a very poor start, with two Laidlaw penalties in the opening five minutes giving the hosts an early cushion.
Edinburgh clearly held the upper hand at the breakdown and, with Munster under the cosh, the penalty count rose steadily.
The visitors duly coughed up another within the range of Laidlaw on the quarter-hour mark, and the home captain dispatched it confidently to widen the gap.
The hosts further hammered home their early dominance when they engineered the space to cross for the game's first try.
The initial break was made by flanker David Denton, who blasted through a weak tackle, the recycled ball finding its way to Scott.
A show of quick feet from the talented centre allowed him to break one tackle, before brushing aside a second to cruise over to celebrate his 21st birthday in style, Laidlaw successfully adding the extras.
With a 16-point advantage, Edinburgh appeared to take their foot of the gas, allowing Munster to establish a foothold in the match.
Keatley soon had his side on the scoreboard with an accurate penalty effort.
His drop-goal attempt moments later however proved less accurate, sliding wide of the upright.
Yet two further penalty conversions in the closing minutes of the half from Keatley ensured that the visitors were still very much in contact at the break.
The home side emerged for the second period with a renewed sense of vigour, an early Laidlaw penalty once again extending their advantage.
And their next try followed soon after, thanks to a delightful line break from winger Lee Jones.
Having unlocked the defence, Jones offloaded to the ubiquitous Laidlaw whose outside pass was gathered by hooker Lawrie, who cantered in to touchdown. Laidlaw was once again able to convert from close range.
Munster offered little in the way of resistance in what was a very off-colour performance, yet they were able to construct a period of sustained pressure in the final quarter.
Having passed up numerous kickable penalties, they were finally rewarded with a try, albeit unconverted, when replacement winger Barnes dotted down in the corner.
It was left to Laidlaw to conclude the scoring in the closing minutes, his fifth successful penalty effort rounding off a surprise win for an ecstatic Edinburgh side.
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