Australia 251 for 5 (Healy 99, Mooney 78, Sutherland 54*, Klass 3-39) lead South Africa 76 (Brown 5-21, Sutherland 3-19) by 175 runs
Australia's quicks defied searing heat at the WACA to tear through an inexperienced South Africa badly missing Marizanne Kapp before captain Alyssa Healy fell agonisingly short of a maiden Test century late on day one.
A tiring Healy, who had been on the field for almost the entire day, was dismissed for 99 when she succumbed to the offspin of debutant Delmi Tucker and was caught and bowled.
But Australia are well on top in the historic first Test between the countries and lead by 175 runs at stumps.
South Africa were routed for just 76 in their lowest ever Test score after being bowled out in 31.2 overs. But they hit back when quick Masabata Klaas produced a spectacular new-ball spell to leave Australia reeling at 12 for 3 in reply.
South Africa's attack were unable to keep up the pressure in 42-degree heat as Healy combined with Beth Mooney in a 155-run partnership to regain Australia's ascendency.
Healy combined with Annabel Sutherland, who took advantage of a wilting South Africa with an unbeaten half-century as the shadows creeped onto the ground.
South Africa's bid for an upset victory to square the multi-format series appears forlorn after a disastrous start to the four-day match.
Playing only their second Test match in a decade, fielding four debutants, South Africa were rocked when Kapp was ruled out due to illness.
A rattled South Africa were unable to cope with the discipline of Australia's quicks, who targeted a dangerous back of a length to devastating effect. South Africa's inexperience against the red-ball, with their XI combining for just seven Tests, was apparent as they fell tamely to loose strokes. Their batters were undone by minimal foot work and too often slashed at deliveries outside the off-stump.
Vindicating Healy's bold decision to bowl first amid fierce heat, speedster Darcie Brown claimed her first Test five-wicket haul while Sutherland and Tahlia McGrath also starred on a green-tinged surface offering movement and bounce.
The dominance of the quicks meant that Healy did not have to call upon Australia's trio of frontline spinners, including Sophie Molineux playing in her first international match in more than two years.
There had been intrigue over the surface, used for the first time this season, but fittingly, in the first men's or women's Test match played at the WACA since December 2017, pace-bowling dominated.
Having won back her spot after missing Australia's last Test in India, Brown steamed in and created a chance almost immediately when opener Anneke Bosch was dropped at third slip by Mooney.
But she was worked over by a fiery Brown as a Kapp-less South Africa desperately needed captain Laura Wolvaardt to overcome her sluggish form on the tour. She was unable to capitalise on a drop from a diving Healy to fall on the next delivery to Brown, who finished a spectacular opening spell with 2 for 5 from five overs.
South Africa appeared to be rallying when Sune Luus and Tazmin Brits dug in to defy Australia for 12 overs. Brits, however, was unable to turn over the strike and crawled to 5 off 48 balls before succumbing lbw to Sutherland in a decision that was overturned on DRS. Tucker had a horror debut when she chopped onto her stumps first ball as South Africa spiralled.
Luus had been the only batter seemingly not overawed by the situation and made a fluent 26, but was lured into a drive by Sutherland to provide more catching practice for the slips.
South Africa offered little resistance and were in jeopardy of being humiliatingly bowled out within a session. They trudged to lunch at 55 for 8, but were unable to get past their previous lowest Test score of 89 against New Zealand in Durban in 1972.
Klaas mounted a fightback with the ball and continued her stranglehold of Litchfield, who edged to third slip after being lured into driving a wide ball. Klass was on a roll and dismissed Ellyse Perry and McGrath cheaply as South Africa stormed back into the contest
But the experience of Mooney and Healy came to the fore as they lifted Australia out of trouble before putting the foot down. Healy was in a typically aggressive mood to race to a 59-ball half-century with a crunching blow through midwicket to race as Mooney shortly after also raised the bat.
South Africa toiled in the baking sun and were seemingly going through the motions until Nadine de Klerk produced a wicket out of nowhere when she had Mooney caught at a wide slip.
Healy looked understandably gassed and she succumbed minutes before stumps, but her team remain firmly in control.