Arjen Robben and Robin van Persie stole the show with two goals each in the Netherlands' 5-1 demolition of Spain in their opening game last week, and the duo once again took centre stage by scoring again in Porto Alegre on Wednesday.
Tim Cahill earlier cancelled out Robben's opener with a contender for one of the greatest goals in World Cup history, before a controversial penalty from Mile Jedinak nine minutes after the restart had Ange Postecoglou's men dreaming of a famous upset.
However, Van Persie quickly quashed those hopes by levelling in the 58th minute with a neat finish inside the area.
And Memphis Depay - who had come on as a substitute for the injured Bruno Martins Indi - broke Australian hearts with a speculative effort that goalkeeper Mat Ryan will feel he should have kept out.
Louis van Gaal's men can now become the first team to qualify for the round of 16 if Group B's other match between holders Spain and Chile ends in victory for the latter or a draw. Australia, meanwhile, face a near impossible task to progress having lost both group games.
Robben's third goal of the tournament in the 20th minute ensured the match exploded into life after a lacklustre opening.
The winger escaped the attention of Alex Wilkinson on the halfway line and surged into the box before drilling a low, angled shot into the bottom right-hand corner.
That lead proved short-lived, however, as Cahill equalised less than 60 seconds later with a goal of the highest quality that will live long in the memory.
Ryan McGowan - playing at right-back in the absence of the injured Ivan Franjic - pinged a superb cross-field pass towards Cahill, who watched the ball over his shoulder and lashed an unstoppable left-foot volley that crashed past the helpless Jasper Cillessen and struck the crossbar before nestling in the net.
It could have been even better for Australia on the half-hour mark, Mathew Leckie fizzed a ball across the area, but the onrushing Mark Bresciano could only side-foot over the bar.
The half ended on a sour note for the Netherlands when Martins Indi was carried off the pitch on a stretcher after a poorly timed challenge from Cahill, who received a booking that means he misses Australia's final group game with Spain.
It got even worse for the Netherlands after the break. Van Persie was first cautioned for an elbow on Matthew Spiranovic that rules him out of the last group game with Chile, before Jedinak put Australia ahead from the spot in 54th minute.
Referee Djamel Haimoudi deemed Oliver Bozanic's cross had been handled by Daryl Janmaat and Jedinak kept his cool to send Cillessen the wrong way.
However, four minutes later, the Netherlands restored parity.
Depay's intricate throughball was collected by Van Persie and the Manchester United striker turned well in the area before rifling a shot into the roof of the net for his 11th goal in his last 10 international appearances.
And, with just over 20 minutes remaining, the Dutch turnaround was complete.
Van Persie's clever run saw the pitch open up for Depay and his speculative effort from 25-yards found its way home via a costly error from Ryan.
Australia pushed forward in the closing stages in desperate search of an equaliser, but the Netherlands easily dealt with the danger to all-but book their place in the last 16.