Vunivalu was one of the surprises in the first Wallabies team of the year with four players in line to make Test debuts in the Rugby Championship match in Pretoria, where Australia have never won.
Co-captain James Slipper has overcome a knee injury and been named alongside young Brumbies utility Tom Hooper, who will start at blindside flanker.
Five-eighth Carter Gordon, lock Richie Arnold and 21-year-old prop Zane Nonggorr will be on the bench for the Loftus Versfeld Test.
Hooper will play alongside co-captain Michael Hooper (no relation) with No.8 Rob Valetini rounding out the backrow.
Vunivali switched codes for the 2021 Super season but failed to have the same impact with Queensland as he did as a premiership winger in 111 games for the Melbourne Storm.
His only Test appearance came last year in the final minutes of the Wallabies clash with England, who were then coached by Jones.
Despite being overlooked from that point by then Australia coach Dave Rennie, Jones saw potential just as he did previously with other code-hoppers Wendell Sailor and Mat Rogers.
He joked during squad selection earlier in the year he would use a cattle prod to get the speedster moving.
Jones said on Thursday the 27-year-old had shown enough to earn selection ahead of NSW winger Mark Nawaqanitawase.
"I've seen him develop some really good habits in Super Rugby and when he's come in and trained with us for the last two or three weeks, every session he's got a bit better," Jones said from South Africa.
"He's an exceptional player, strong in the air, big guy, got good pace.
"I've got no doubt he's going to do a good job for us on Saturday."
Jones said what he liked about 22-year-old Hooper was he "rips in", with physicality a key ingredient in trying to topple the Springboks.
It's a massive challenge for Reds prop Nonggorr, 21, who got the nod with Taniela Tupou requiring more training minutes after his Achilles injury.
Slipper was in doubt after a training mishap but will make his 128th Test appearance alongside Waratahs hooker David Porecki and Brumbies skipper Allan Alaalatoa at tighthead prop.
"It's been a challenging week, had a bit of mishap on Tuesday but I get to run today make sure it's all good but I'm pretty confident I'll be playing," Slipper said.
Nick Frost and France-based Will Skelton are the starting locks.
Nic White will reunite with Quade Cooper in the halves while star inside centre Samu Kerevi will return from a hamstring issue via the bench, leaving Reece Hodge to combine in the midfield with Len Ikitau.
Marika Koroibete is on the left edge and Tom Wright at fullback.
The Springboks have sent a number of their big names to New Zealand to prepare for the upcoming clash with the All Blacks but Jones said whomever they fielded at Loftus would present a massive challenge.
"We're really only worried about ourselves, we're focused very much on ourselves.
"We're a new team, we want to play our style of rugby, and we know whatever team that runs out at Pretoria on Saturday is going to play with the pride of South Africa behind them and we need to meet that challenge."
Wallabies: James Slipper (co-capt), David Porecki, Allan Alaalatoa, Nick Frost, Will Skelton, Tom Hooper, Michael Hooper (co-capt), Rob Valetini, Nic White, Quade Cooper, Marika Koroibete, Reece Hodge, Len Ikitau, Suliasi Vunivalu, Tom Wright. Res: Jordan Uelese, Matt Gibbon, Zane Nonggorr, Richie Arnold, Pete Samu, Tate McDermott, Samu Kerevi, Carter Gordon.
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