On a chaotic morning when Steve Smith ruled himself out with a neck injury, Australian captain Pat Cummins sent the Proteas in on a straw-coloured pitch under largely blue skies.
Australia's start then became their worst after electing to bowl first in a game in 56 years, since Bill Lawry sent England in at the WACA in 1970 and they put on 171 for the first wicket.
The decision almost immediately appeared questionable on Tuesday, with Aiden Markram making a statement in pulling Cummins for a six in the seventh over.
His opening partner Marques Ackerman hit another one over long-off from Nathan Lyon, with Australia's spinner brought on after just 10 overs.
And with the tourists looking as flat as the Newlands pitch before lunch, Ackerman picked Cummins up over fine leg for a six and clipped the next ball for another boundary.
Australia's morning was summed up when Markram hit Mitchell Starc straight to cover on 39, only to see Travis Head put down the simplest of catches.
Starc's reaction, as he put his collar between his teeth, said it all.
In all Markram (82) and Ackerman (56) hit 23 boundaries in the first session, as Australia employed two men back on the legside from within the first hour.
It came after the tourists opted to go without Scott Boland after his five-wicket haul last week and bring back Lyon, as one of four changes to the side.
Cummins said at the toss he believed there was "a bit of moisture" in the wicket, while Proteas captain Temba Bavuma said his side was happy to bat first.
The Proteas' glee showed.
Markram punched a ball past cover for four off Starc in the third over and South Africa kept going from there.
By the time lunch was near, the right-hander was dispatching good length balls to the boundary from the likes of Josh Hazlewood, as he brought up his 50 from 81 balls.
Ackerman raised his half century off 62 balls, then set about hitting Starc for four boundaries in one over before lunch through mid wicket and the gully.
Australia's return to Cape Town for a Test for the first time since the 2018 ball-tampering scandal had began in dramatic fashion, with Smith's neck the point of focus.
The 37-year-old arrived before the rest of the team and was spotted appearing frustrated in the nets, before making the call that he was not right to play.
That prompted Cummins to say at the toss that Australia "had to look elsewhere", with Josh Inglis called in for his first Test since last summer.
Boland, Nic Maddinson and Beau Webster were dropped following last week's thrashing in Gqeberha, with Lyon, Cooper Connolly and the fit-again Cameron Green all coming in.
The four changes are the most Australia has made mid-series since the ball-tampering scandal.
South Africa can take top spot in the ICC rankings from Australia with victory at Newland
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