The Dutch women were eliminated by Germany in their quarter-final of the 2400m, six-lap race.
It soon became a double dose of disappointment for the Dutch when 5000m champion Sven Kramer and his two partners were beaten in the men's semi-finals by a US trio led by 1,000m bronze medallist Chad Hedrick.
Kramer, who missed a certain gold in the 10,000 metres when his confused coach ordered him to change to the wrong lane and he was disqualified, said he and his team-mates frittered away precious time.
"Halfway through we had a lot of miscommunication," Kramer said about the surprising result in the eight-lap race around the 400m Richmond Olympic Oval.
Kramer, the 5000m champion, was feeling strong but team-mate Jan Blokhuijsen was fading. During the race, a three-man team take turns leading the way.
"Blokhuijsen was not giving away the top for me," said Kramer.
"Finally, when I came on top he was yelling I was going a little too fast. After that, Mark (Tuitert) was giving me a sign to go back and push Jan. That's pretty hard. That's a big mistake."
The Dutch began to fall steadily behind the Americans and Hedrick, who built a lead of more than 1.5 seconds going into the last lap.
With a mighty push, the Dutch made up more than a second on the final lap but fell short by four-tenths of a second.
"It's a big upset," Tuitert, the 1500 metres champion, said. "We didn't do our best. We had a great team."
Kramer came to Vancouver confident of three gold medals and capping his Olympics with victory in the team pursuit to make up for his fall in the 2006 semi-finals which deprived the bronze-winning Dutch of a shot at Turin gold.
"I came to the Olympics for three gold medals. I have just one now," said Kramer, who will skate in the bronze medal race against Norway. "It's a little strange. I expect more."
The Americans set up a gold medal final against Canada's men while the American women also sprung a surprise to knock the Canadians out of the running.
The Canadian world-record holders, featuring 1000 metres champion Christine Nesbitt and double medallist Kristina Groves, lost their three-skater quarter-final against the United States by a scant five-hundredths of a second.
"I had no idea we had won," American Nancy Swider-Peltz said. "With all the loud cheering I thought we were way behind."
The US women will race against Germany while Japan and Poland meet in Saturday's other semi-final. Japan beat South Korea and Poland defeated Russia in the quarters.