The all-rounder, moved up the order to open the batting in place of Rashada Williams, took the game to New Zealand from the start and pummelled 16 fours and a booming six in her 128-ball 119 at Mt Maunganui on Friday.
The 23-year-old Barbadian returned to take 2-41 with her offspin and set back the New Zealanders in their bid to chase down 260 runs for victory in front of a sparse, COVID-19 restricted crowd.
Sloppy West Indies fielding gave Sophie Devine at least two lives and the New Zealand captain took full advantage with a battling 108 that kept the hosts in with a sniff of victory.
Seamer Chinelle Henry finally ousted the home captain with a brilliant juggled catch off her own bowling to set up a dramatic final five over under the Bay Oval lights.
Katey Martin (44) and Jess Kerr (25) needed six runs from the final six deliveries but Deandra Dottin, bowling her first over of the match, dismissed them both and ran out Hannah Rowe on the penultimate ball to leave New Zealand 256 all out.
"I thought we were right in it until the last over," said Devine.
"You don't get much more clutch than a bowler coming on in the 50th over and doing what Dottin did. So full credit to them but we've got to move on quickly."
Matthews said coach Courtney Walsh had called her on Thursday and told her she would be opening in place of Williams, who was ruled out of the match by concussion protocols.
"Just pretty happy that I could get some runs up top," said Matthews. "Definitely my best score, definitely up there with one of the best innings."
The tournament, delayed by 12 months because of the global health crisis, pitches all eight teams in an opening round-robin with the top four progressing to the semi-finals.
Australia, who are favourites to win a seventh title, open their campaign against holders England in Hamilton on Saturday.Â
