Munro, with a rollicking 104 off 53 deliveries, became the first player to hit three centuries in international Twenty20 cricket as New Zealand posted an imposing 243 for five, their highest Twenty20 total.
The West Indies reply began disastrously with openers Chadwick Walton and Chris Gayle out without scoring in Tim Southee's opening over.
Their innings folded at 124 for nine in 16.3 overs with Shai Hope unable to bat after being injured while fielding.
With the West Indies two down for one run after five balls, Andre Fletcher did his best to rebuild the innings and ensured the tourists kept up with New Zealand's run rate for the first eight overs.
But the introduction of spin saw Fletcher's innings come to an end. He was bowled by Ish Sodhi for 46, and the momentum fizzled.
From 80 for four after eight overs, the last five West Indies wickets fell for 44 runs in 51 balls.
He faced 53 balls, smacking 10 sixes and three fours.
With previous centuries against India and Bangladesh, he moved ahead of a group of four players, including Gayle, who have two international T20 centuries.
Munro and Martin Guptill gave New Zealand a flying start to their innings with a century partnership.
It was a timely return to form for Guptill with 63 off 38 balls after struggling against the West Indies earlier in the series.
Rayad Emrit, selected to make his T20 debut two months short of his 37th birthday, celebrated by breaking the New Zealand opening stand when he had Guptill caught behind.
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