There was heartbreak for British fans as Matthew Hudson-Smith was pipped at the line in the men's 400m final, with American Quincy Hall storming to a maiden gold on his Olympic debut.
A four-time European champion, Hudson-Smith was the favourite heading into the race, after clocking the fastest time of the year just three weeks ago.
London 2012 winner Kirani James was also in resurgent form, running 43.78 seconds in the semi-final to lead everyone.
But the 31-year-old could only watch the podium fight in front.
Hudson-Smith was the first one to exit the final bend, but with the finish line within reach Hall charged into the lead and won in a personal best of 43.40 seconds.
The Briton nearly lost his silver to Muzala Samukonga, the Zambian who came back only three-tenths of a second behind Hall.
Also on the track, Morocco's Soufiane El Bakkali became the first man in nearly a century to win back-to-back 3,000m steeplechase gold medals.
The feat didn't come easy as the trio on the podium were separated by less than half a second.
Over in the field, Jamaica's Roje Stona claimed an unlikely victory in the men's discus throw.
He edged out Lithuania's Mykolas Alekna, who broke his father Virgiljus' Olympic record before Stona extended the mark further.
And Australia's Nina Kennedy dethroned American defending champion Katie Moon in the women's pole vault after clearing 4.90m.
That was 5cm higher than both Moon and Canada's Alysha Newman, who got bronze.