In a dominant display in St Vincent, Voll unloaded with six sixes in her knock to bring up her first T20 century to help Australia to 7-211.
Rain then stopped the hosts' chase at 3-61 after 10 overs, handing Australia a 40-run win on the DLS Method in their last T20 match before heading to England for the World Cup in June.
A powerful striker of the ball at the top of the order, Voll is expected to play a key role for Australia following Alyssa Healy's retirement.
And the team's desire to play more fearless cricket was on show in her 101 in the third T20 against West Indies on Monday (Tuesday AEDT).
She used her feet well to spinners and took them on down the ground, making her intent clear when she hit Shawnisa Hector over long on in the third over.
Three more sixes came off the slog sweep later in the innings, with the right-hander offering the slower bowlers barely any respite.
The 22-year-old then brought up her 52-ball hundred when she slashed Deandra Dottin down to the deep-third boundary, before being bowled on the next delivery she faced by Hayley Matthews.
Voll's century century marked the third fastest of an Australian behind Alyssa Healy against Sri Lanka in 2019 and Meg Lanning in that year's Ashes.
Sophie Molineux also hit 25 off 12 late in her first bit of batting or bowling for the series, with officials playing it safe on the new captain's return from back pain.
Nicola Carey struck an unbeaten 24 off 20, helping her push to play ahead of vice-captain Tahlia McGrath in England.
Megan Schutt had Qiana Joseph with the second ball of the West Indies innings, as the veteran and debutant Lucy Hamilton both claimed 2-11 from two overs before the rain hit.
Australia and West Indies will face off in a three-match ODI series in St Kitts, before Australia have matches against South Africa in England ahead of June's World Cup.
FASTEST T20I CENTURIES BY AUSTRALIAN WOMEN:
* Alyssa Healy: 46 balls v Sri Lanka, 2019
* Meg Lanning: 51 balls v England, 2019
* Georgia Voll: 52 balls v West Indies, 2026
* Meg Lanning: 53 balls v Ireland, 2014
* Beth Mooney: 54 balls v Sri Lanka, 2019
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