Veteran Teun de Nooijer marked his 450th appearance with a goal as the Netherlands won the battle of the European heavyweights against Germany 3-1 in Group B to qualify for the men's Hockey semi-finals.
The 36-year-old's 218th international strike was pivotal, coming just 25 seconds after half-time to give the Dutch a lead they never let slip.
It leaves defending Olympic champions Germany requiring a point from their final match against New Zealand to join them in the last four.
Elsewhere, Great Britain produced a brilliant second-half comeback to stun world number ones Australia, who appeared to be coasting towards the semi-finals.
The hosts were 3-0 down early in the second half before they made their charge in exhilarating fashion to leave the Kookaburras wondering what had hit them.
Two goals from Russell Ford and another from Mark Knowles had seemingly put Australia in control but Jonty Clarke began the fightback before captain Barry Middleton and James Tindall completed the recovery as it ended 3-3.
There was arguably even more drama in the late game, as Spain produced an astonishing last six minutes to score three times and keep alive their own semi-final hopes, beating Argentina 3-1.
Trailing to Lucas Vila's 55th-minute goal, the Europeans were heading out of medal contention in Group A until a sudden turnaround thrust them back in.
Spain scored three goals without reply as Pau Quemeda, Miguel Delas and Eduard Tubau snatched victory.
New Zealand's 1-1 draw with Belgium was unsatisfactory for both sides as it ended any distant hopes they had of making the semi-finals, while Pakistan snatched a 5-4 victory with two late goals in the highest-scoring match of the tournament against South Africa.
India's miserable run at the Olympic Games continued as they slumped to a fourth successive defeat, 4-1 against the Republic of Korea, to remain the only team in the tournament without a point.