Currently ranked number one in the world and being 2008 Beijing Games bronze medalists, Australia showed their class as world number 12, South Africa, struggled to gain any momentum in the Aussies' half.
SA started the match well, restricting Australian possession and held on to the ball for long periods as they looked to settle into their structure and rhythm.
Australia eventually drew first blood when Jamie Dwyer converted a penalty stroke past SA goalkeeper Rassie Pieterse, after an infringement in the area.
Pieterse was called into action from the off, as Australia saw two penalty corners (PC) saved by the defensive unit.
The South Africans conceded two further PCs as Australia came into the game and looked to stamp their authority, with Pieterse again saving well to deny the Kookaburras a second goal.
Australia appeared to have doubled the lead six minutes from time when they 'scored' from their fifth PC, but SA skipper Austin Smith called for a video referral which was upheld after the ball clearly came off a foot on the way into the net.
Four minutes later, however, the Aussies scored through Matthew Butturini, after Dwyer ran into the SA area before lofting a shot towards goal, which Butturini glanced to send the ball home.
After leading 2-0 at half time, Australia looked content to sit back and let their opponents do the work while sweeping up any chances SA had to get back into the game.
SA struggled to break down the Australia defence and gave away three further PCs midway through the second period, two of which were converted by Christopher Ciriello in the 44th minute, and by Dwyer two minutes later to grab his second of the day.
At 4-0 up, the Australians pushed for another score but found it difficult to score from open play as SA held firm but gave away too many set-pieces in their area.
Dwyer completed his hat-trick with 12 minutes to play, as he scored a second penalty stroke after Pieterse was adjudged to have tackled the man and not the ball.
Australia rounded-off a dominant performance with eight minutes left to play as Glenn Turner received a well-timed pass from Matthew Gohdes, leaving Turner with an open net into which he eased home.
SA's next fixture is against Great Britain on Wednesday, where they will need to get a result to stand any chance of progressing through to the next round.
Olympic Games field hockey results on Monday:
Men
South Korea 2 New Zealand 0
Australia 6 South Africa 0
Spain 1 Pakistan 1
Netherlands 3 India 2
Great Britain 4 Argentina 1