It took just 11 minutes for the South American side to get their tournament up and running courtesy of Alexis Sanchez's goal from close range following an Eduardo Vargas knock down.
Two minutes later La Roja doubled their lead when Vargas's run across the box left Jorge Valdivia in space to place the ball into the top left corner of the net.
It looked as though Australia were going to be in for a long night, but striker Tim Cahill reduced the deficit on the 35-minute mark when he outjumped Gary Medel to make it 2-1.
Cahill very nearly found the net once more before the interval when Mathew Leckie prodded a ball through to him, but his angled drive was well kept out by Claudio Bravo.
Shortly after the restart the former Everton man thought he had drawn his side level, only for his header to be correctly ruled out for offside.
Bravo was called into action once more just short of the hour-mark to keep out Mark Bresciano, who steered a left-footed strike towards to bottom corner of the net which had to be kept out.
Moments later Chile hit back when Sanchez threaded a pass behind the Australian defence for Vargas to latch onto, and the forward lifted the ball over Matthew Ryan, only for Alex Wilkinson to clear off the line.
The Socceroos pushed for a leveller, but they were left exposed allowing Jean Beausejour to round off the scoring at the death with a strike from 20 yards to seal the three points.
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