West Indies 213 for 3 (Matthews 132, Taylor 59) beat Australia 212 for 6 (Perry 70, Litchfield 52*, Matthews 3-36) by seven wickets
After the first innings, it appeared Phoebe Litchfield would be the performance talked about as she equaled the record for the fastest fifty in women's T20Is off 18 balls, but that was put well in the shade.
Matthews, who was left stranded on 99 in the opening match of the series, surged to a 53-ball century this time and carried her team to the brink when she finally fell for a magnificent 132 off 64 balls having taken four consecutive boundaries off Jess Jonassen in the penultimate over.
It left West Indies needing 9 off 7 deliveries which Shemaine Campbelle and Chinelle Henry were able to scamper in the final over against Ash Gardner with a ball to spare when Australia had to have an extra fielder inside the ring due to a slow over-rate.
Taylor had overcome a sluggish start to play a vital hand with 59 off 41 balls in a stand of 174 in 14 overs with Matthews. Australia's bowlers had no answers and they paid the price for dropping Matthews twice, on 30 and 87. Their tactics will also have to be called into question with Matthews repeatedly exploiting an unprotected off-side boundary.
She scored 19 off her 25 boundaries on the off side with 77 runs coming from cover drives and in all 110 of her runs came in fours and sixes.
Overall, it was the highest scoring women's T20I in history with 425 runs and Matthews collected her seven consecutive player-of-the-match award.
West Indies had made the perfect start to the game when Alyssa Healy fell first ball, spectacularly caught at backward point by Campbelle and Australia were 7 for 2 when Tahila McGrath was bowled by an excellent delivery from Matthews.
From there, however, the home side rebuilt through a stand of 70 between Beth Mooney and Ellyse Perry before two more wickets fell in quick succession to leave them 89 for 4 when Litchfield walked in.
There had been some surprise when she was preferred to Grace Harris at No. 6 for this series, but Australia have wanted to try a left hander in that position. It will be difficult to shift her now. She collected her first six from her second delivery when she advanced at Aaliyah Alleyne and pulled over deep backward square. That was followed by consecutive sixes off Henry, the second as she advanced and drove over long-off.
For a little while she lost the strike as Georgia Wareham took over with her own powerful strokeplay, but Litchfield found the boundary from five of her next six deliveries with her fifth six equaling the record.
A brutal stand of 66 off 22 balls between Litchfield and Georgia Wareham, who made 32 off 13, enable the home side to put on a power packed finish that produced 88 runs from the last five overs - a record for where complete data is available. Astonishingly, it ended up coming in a losing cause.