The Kookaburras have claimed silver for the fourth time at an Olympics, with Belgium claiming victory in the men's hockey final following a thrilling penalty shootout.
After the score was deadlocked at 1-1 at the end of the regulation time, the gold medal went the way of Belgium when they finished 3-2 ahead in the shootout at Oi Hockey Stadium.
The Kookaburras had the chance to draw level at 3-3 when Jake Whetton was called up to take a penalty.
His first attempt was thwarted by Belgian goalkeeper Vincent Vanasch, however the Australian was allowed another penalty when an unintentional foul was found upon video review.
Vanasch had made contact with Whetton's leg, but the Kookaburras star could not find the back of the net with his second attempt, the miss clinched Belgium's win.
Florent van Aubel had earlier scored Belgium's goal during the third quarter, with Tom Wickham providing the equaliser for the Kookaburras.
"Everyone is a bit disappointed," Kookaburras captain Eddie Ockenden told Channel Seven.
"We came here to win. We didn't quite get there but we feel like we played pretty well … shootouts are tough. It didn't go our way."
It is the first time Belgium, the world champions, has won the men's hockey gold medal at an Olympics.
The Kookaburras had previously won silver in 1968, 1976 and 1992. They have now claimed 10 medals in men's hockey.
Earlier, India clinched the bronze medal with a 5-4 win over Germany in the playoff for third and fourth.
The opening quarter was played at a furious pace, with Belgium enjoying slightly more possession than the Kookaburras.
Neither side could penetrate their opponent's defence, but early in the second quarter Cedric Charlier launched a well-timed shot that forced Kookaburras goalkeeper Andrew Charter into action.
Charter comfortably made the save, however his reflexes were tested only minutes later when Antoine Kina fired the ball at goal.
The Kookaburras' defence was put under pressure again inside the final six minutes of the quarter, with Belgium earning back-to-back penalty corners.
The Australians survived both and made sure to keep a clean sheet through to half-time, but the Red Lions landed a blow in only the second minute of the third quarter.
Van Aubel beat Charter to score to open the scoring, the goal lifting Belgium's intensity in attack.
The Kookaburras did now bow their heads, however, and they finally earned a penalty corner with five minutes remaining in the quarter.
Jeremy Hayward did little wrong with his effort on goal, but Vanasch kept the Kookaburras at bay and the score remained 1-0.
The Kookaburras were not to be denied and they were rewarded in the second minute of the final quarter.
They capitalised on an entry in Belgium's circle, with Wickham equalising at 1-1.
The Kookaburras had the momentum after Wickham's goal, but the two sides could not be split ahead of the full-time siren, forcing the final to be decided by a shootout.
