The Netherlands came back from an early deficit — German forward Christopher Zeller scored in the third minute from a penalty corner. Bob de Voogd and Mink van der Weerden scored the other Dutch goals.
The result means the Netherlands are the first team to qualify for the medal round.
"Overall I'm very happy," Dutch coach Paul van Ass said. "But although we are glad, we know that we have just made it to the semifinals, and I do think we will meet the Germans again in this tournament."
Britain staged a thrilling comeback Sunday to draw 3-3 with No. 1-ranked Australia, scoring three second-half goals to salvage a draw.
Russell Ford scored twice in quick succession for Australia early in the first half, and captain Mark Knowles added a third in the 41st minute.
Minutes later Jonty Clarke scored for Britain. With the crowd behind the home team, captain Barry Middleton scored in the 52nd minute from a penalty corner, and James Tindall got the equalizer in the closing minutes.
"At 3-0 down we could have dropped our heads ... but we never let that happen," Middleton said. "As the game went on we just built confidence in ourselves. The crowd definitely helps."
"It's disappointing, but that's the sport ... We have to be a goal better, and we weren't today," Australia coach Ric Charlesworth said.
In other matches Sunday, Pakistan beat South Africa 5-4, South Korea defeated India 4-1 with three late goals, and Belgium and New Zealand drew 1-1, meaning neither team will advance to the knockout round.
In the day's last match, Spain fell a goal behind to Argentina with 15 minutes to play and then scored three goals in the last five minutes to win 3-1.
Captain Sohail Abbas and Waseem Ahmad scored late goals to give Pakistan a comeback win over South Africa. The win in a match which featured four lead changes moved Pakistan into third place in its group, level with Australia and Britain, who play each other later Sunday.
South Africa opened the scoring in the second minute from a field goal by Thornton McDade and Pakistan's Abdul Hasseem Khan equalized in the 20th minute.
Justin Reid-Ross put the South Africans back in front but Khan put Pakistan ahead again with a goal in the 25th minute.
Reid-Ross' second goal and another by Wade Paton gave South Africa a one-goal lead before Pakistan's late scoring surge.
"It was a great match and we had a plan that if we could win that match, we would have a chance to reach the semis," Khan said. "We played our best and at the beginning there was quite a lot of pressure but at the end we played well."
Eight-time Olympic champion India has not taken any points from its four games in London. The scores were level with 11 minutes to go after early goals by Jang Jong-hyun of South Korea and Gurwinder Singh Chandi for India.
But two goals from penalty corners by South Korea defender Nam Hyun-woo and one by captain Lee Seung-il gave the team the late victory.
Balbir Singh, who won gold with India's field hockey team in the 1948 London Olympics and twice after, was watching the game.
"(We are) sorry we could not get a win for him," said Chandi. "We will be meeting him after the game. We have a lot of respect for him."
Belgium took the lead over New Zealand with a 48th-minute field goal by Tom Boon, but Nicholas Wilson equalized six minutes later.
Belgium was the stronger side, with 18 chances at goal compared to New Zealand's eight.