Spain's bid to add Olympic gold to their world and European titles ended in failure on Sunday with a shock 1-0 loss to Honduras.
Jerry Bengtson's seventh-minute header at St. James' Park, the striker's third goal in two games, condemned Spain to an early exit following their opening defeat by Group D leaders Japan.
In a fractious match featuring 13 bookings, Spain's Iker Muniain hit the post and Rodrigo the bar, and a host of Spanish players converged upon referee Juan Soto Arevalo after the Venezuelan denied them a late penalty.
Spain coach Luis Milla insisted his side had been unlucky.
"All that was lacking today was the goal. I don't want to say too much, but we feel there should have been a penalty," he said.
Bengtson scored when he rose high to power in Roger Espinoza's driven cross past Manchester United goalkeeper David de Gea.
"We played so well to beat Spain," said Bengtson. "It's very nice that we heard the crowd supporting us and shouting 'Honduras, Honduras'."
Gold-medal favourites Brazil came from a goal behind to beat Belarus 3-1 with Neymar turning on the style at a packed Old Trafford on Sunday.
Belarus took a shock lead, in front of a crowd of more than 66,000 at the home ground of English giants Manchester United, through Renan Bardini Bressan's eighth-minute header.
But from then on Brazil, five-times world champions but still seeking a first Olympic gold, saw Neymar take charge.
He crossed for AC Milan star Pato to equalise, before he put Brazil in front with a brilliant 65th minute free-kick and then set up Oscar for the third goal.
Meanwhile Great Britain enjoyed their first Olympic win since 1960 with a 3-1 defeat of the United Arab Emirates at Wembley.
After Manchester United veteran Ryan Giggs had become the oldest goalscorer in Olympic history at the age of 38, Rashed Eisa equalised for the UAE.
But goals from Scott Sinclair and Daniel Sturridge eased the hosts' nerves.
"Ryan brings respect," said Great Britain manager Stuart Pearce, whose side could only manage a 1-1 draw with Senegal first time out.
"That's a word that's used cheaply nowadays, but the way he handles himself on and off the pitch is outstanding and we were delighted he got a goal this evening."
Meanwhile 10-man Senegal opened up Group A with a shock 2-0 win over Uruguay, teenager Moussa Konate scoring twice either side of Abdoulaye Ba's first-half dismissal for a foul on Luis Suarez.
Japan qualified for the quarter-finals with a 1-0 Group D win over Morocco secured by Kensuke Nagai's 84th minute goal.
Asian rivals South Korea also enjoyed a 2-1 win over Switzerland to draw level with Group B leaders Mexico, who beat Gabon 2-0 thanks to two goals from Tottenham's Giovani dos Santos.
Egypt's last-eight hopes suffered a setback when they were held to a 1-1 draw by New Zealand.