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Belgium have defeated Australia 4-2 in a penalty shootout to win a dramatic Pro League hockey opener at Sydney Olympic Park.

The Kookaburras have started the year with a penalty-shootout loss to Belgium at Sydney Olympic Park, where a tense tussle between the world's two best hockey teams has lived up to its billing.

Australia and World Cup holders Belgium meet again on Sunday as they battle this weekend for the world No.1 ranking.

The prospect of their epic rivalry extending into the gold medal match of the Tokyo Olympics looms large, as evidenced by Saturday night's cracking contest that the visitors won 4-2 on penalties.

Captain Thomas Briels's second-quarter goal gave Belgium the early advantage in the Pro League opener, a rematch of last year's final that the Kookaburras won 3-2.

Tom Craig and Jeremy Hayward scored in a drama-packed final term to put Australia in front on the scoreboard, only for Alexander Hendrickx's deflection to level the score at 2-2 with a tick over a minute left.

The hosts were a man down for the final seven minutes of the contest after Tim Brand was given a yellow card following a video review of his goal-mouth tangle with Loick Luypaert.

"The great thing about playing Belgium is you find out a lot about the guys. If we're playing one of the lesser ranked teams in the world, we might win easy but we wouldn't learn as much," Kookaburras coach Colin Batch said.

"We were playing one of the best teams in the world and they're well practiced, well drilled. They've had a team that has played together for a long time, so perhaps they settled their game a bit quicker than us.

"But I was pleased with the way we approached the second half, we were able to turn the game around ... and we're certainly in a better position than we were at this time last year."

Batch admitted Brand's booking changed the game.

"At that stage we had quite some momentum," he said.

"I haven't had a good look at it. It's gone to video and they've deemed a 10-minute yellow, so we just have to wear it."

Australia defended desperately in the final stages and goalkeeper Andrew Charter produced a couple of good saves before conceding the equaliser.

Belgium keeper Vincent Vanasch excelled in the shootout, setting the tone when he stopped Australia's opening shot from Brand.

Successful conversions from Florent van Aubel, Simon Gougnard, Victor Wegnez and Arthur van Doren sealed the result.