Just as their path to gold had been blown wide open, the Kookaburras' Olympic men's hockey campaign came crashing down in a 2-0 quarter-final loss to the Netherlands.

Two second-half goals were enough for the Dutch to exact some revenge on Sunday after losing in a shoot-out at the same stage to Australia in Tokyo three years ago.

The Kookaburras entered as offensive powerhouses and Pro League champions, among the fancies to end a 20-year drought and claim a second Olympic title.

But they were barely able to fire a shot thanks to some merciless Dutch circle defence and little luck.

The loss came after defending champions Belgium were upset by No.8 Spain, who will now play the Dutch for a spot in the final.

India began the day of upsets with a shootout defeat of Great Britain, scores tied 1-1 at full-time despite them playing most of the contest with 10 men after an early red card.

India will play Germany, who beat Argentina 3-2, in the other semi-final.

"It was a bit stop-start but, you could say that about everyone though," Kookaburras coach Colin Batch said of the Kookaburras' up-and-down tournament.

"You've just got to be at your best when it counts and the Netherlands played a really good game today.

"A very even first half, they took their chances then defended very well.

"We were well prepared to perform well. Some people might say we underperformed ... but there are marginal differences between losing and winning and today didn't go our way."

Australia pulled 250-game goalkeeper Andrew Charter for the final four minutes, replacing him with whippet Jake Whetton as they desperately chased goals.

But they weren't rewarded, a penalty corner for a Dutch foot missed and Australia unable to review after burning their only referral in the first quarter.

They'd had just six shots on goal before that and, until the final five minutes, one penalty corner.

That corner did draw a superb save from Dutch 'keeper Pirmin Blaak, who got his right leg wide enough to stop a low-flying Blake Govers rocket that could have sent the Australians on their way.

Instead, Duco Telgenkamp's diving deflection off a penalty corner needlessly given away by an impeding Lachie Sharp broke the game open in the third quarter.

The dagger came later in the term, Thijs van Dam released down the left wing, darting back infield and smoothly depositing his shot into the left sideboard.

"It felt like we were in it, it's disappointing ... I never thought we would (lose) so it's hard," Kookaburras great and opening ceremony flagbearer Eddie Ockenden said.

"It sucks."

Ockenden, in his record fifth Olympic campaign, remains open to playing on.