Valverde was supposed to wait for Freire, according to team orders, on the final ascent of the Cauberg but instead launched out in a lone pursuit of winner Philippe Gilbert that netted the rider from Murcia his fourth visit of his professional career to the road race world championship podium, albeit never for gold.
Freire strongly criticised Valverde for riding for himself, but Valverde responded by saying it was the only option he had.
"We had talked about racing for Oscar, but when I saw Gilbert was getting a gap, I responded to that attack.
"So we left him (Freire) alone? Gilbert was a long way off and we wouldn't have caught him even if we had started to chase. In fact, if I hadn't doubted for a while, I'd have gone with Gilbert, not after him. I should have chased after him straight way."
Valverde agreed that the Spaniards had agreed pre-race to protect Freire - fourth in Amstel this spring, which finished on the Cauberg - in the last lap, "but if I had stayed with him, we wouldn't have got a medal.
"I did the right thing trying to chase down Gilbert. Boasson Hagen and [Alexandre] Kolobnev [Russia] had already attacked. Bloody hell, it was bronze, but it could have been gold."
By the time he reached the summit of the Cauberg, Valverde said, "Gilbert had a good distance, we weren't working together and we knew we were fighting for silver or bronze. There wasn't any time for more. There wasn't enough distance. And I couldn't have taken Oscar with me.
"We should be happy, we've got a medal for Spain and that's what matters."
Edvald Boasson Hagen (Norway) said he had to "thank his teammates for keeping me up there, I had to take my chance today.
"It was impossible to catch Gilbert when he attacked, I was a little bit too far behind. I hoped other guys would close the gaps and that didn't happen. Only Valverde made a move and I went after him. Silver was the best I could have got today.
"I was feeling good throughout the race, not just on the Cauberg, although to be honest I thought the race would be harder than it actually was."
One team manager that was particularly delighted, on a personal level, that Boasson Hagen had done so well was Dave Brailsford, Team Principal at the Norwegian's trade team, Sky.
"With my Sky hat on, it's great to see Eddy get a medal," Brailsford told Cyclingnews. "He's a bit up and down sometimes, but when he's good, he's unbelievably good, and that was a great ride for him."
Brailsford also had nothing but praise for Gilbert, saying, "When you think who in their careers should have the rainbow jersey, Gilbert certainly deserves it and I don't think anybody could deny he's a worthy winner who will wear it with pride."