The Proteas captain struck a majestic 169 off 143 balls to help her side to a total of 319-7 before Marizanne Kapp then took career-best figures of 5-20 as England were bowled out for 194.
After being put in to bat, Proteas opening pair of Wolvaardt and Tazmin Brits put on on a partnership of 116.
It would have settled any nerves in the dressing room after they were bowled out for just 69 against England in their opening match of the tournament.
Brits lost her wicket in the 23rd over, bowled by Lauren Bell, for 45 to trigger a mini-collapse that saw the Proteas lose three wickets for just three runs.
Anneke Bosch lasted three balls before being bowled by Sophie Ecclestone before Sune Luus was sent packing by England skipper Nat Sciver-Brunt to leave the Proteas 119-3.
Wolvaardt then combined with Kapp for a crucial 72-run partnership with Kapp aggressively making her way to 42 off 33 balls.
Kapp (42) then skied Ecclestone going for another big shot and Proteas lost another three wickets in quick time to leave them on 202-6.
All the while Wolvaardt was going on her merry way at the other end and brought up her century off 115 balls before cutting loose in the final 10 overs.
The Proteas captain slammed four sixes and found a good partner in Chloe Tryon as the duo put on 89 from just 47 deliveries to take the side over the 300-run mark.
Wolvaardt was dismissed with two overs remaining but walked off to a standing ovation with every one of the England players coming to her to offer a handshake.
Tryon remained unbeaten 33 while Nadine de Klerk was 11 not out as the Proteas would have felt might pleased with the total.
Kapp then rattled England with two wickets in the first over of the run-chase before Ayabonga Khaka got another scalp in the second over to with the score reading 1-3.
Sciver-Brunt (64) and Alice Capsey (50) put on 107 for the fourth wicket but the Proteas were not to be denied as Kapp returned to in the middle overs to dismiss the England skipper.
The Proteas allrounder then cleaned up Charlie Dean and Sophia Dunkley to complete her second five-wicket haul in her ODI career.
England captain Harry Brook says his dropped off catch off Sanju Samson went a long way to his team losing their T20 World Cup semifinal against co-hosts India in Mumbai.
Sam Curran feels England need to be on top of their game if they are to beat India and silence the home crowd in Thursday's T20 World Cup semifinal in Mumbai.
Will Jacks says England are relishing life under Harry Brook's captaincy after booking their place in the semi-finals of the 2026 T20 World Cup with a perfect Super Eights record.
England completed an unbeaten Super 8s phase at the T20 World Cup after a thrilling four-wicket victory in the final over against New Zealand in Colombo on Friday.
