Britain's Chris Froome finished second overall as Spain's Juan Jose Cobo was crowned Vuelta a Espana champion after the 59-mile (95.6km) stage to Madrid.
Fellow Briton Bradley Wiggins took third place overall as Slovakia's Peter Sagan won the final stage following a three-way sprint to the finish line.
Cobo held a 13-second lead over Froome and defended it during the final stage.
Robert Millar was the only previous Briton to claim a podium finish in the Vuelta, finishing second in 1986.
Froome's result is all the more surprising because his previous best result in a major stage race was 36th overall in the Giro d'Italia in 2009 and he was entered as a "domestique" to support Triple Olympic champion Wiggins in the mountains.
"The last three weeks have been an unforgettable experience. It's actually quite overwhelming," said 26-year-old Froome.
"If three weeks ago you had told me that I would be standing on the podium in Madrid I wouldn't have believed you. This has really been a life-changing experience.
"I've moved up a lot. I think I've learnt a lot riding alongside Bradley, like learning how to conserve my energy instead of going off on crazy attacks and just being more consistent and being there on the big climbs."
Froome, however, remains unsure where his long-term future lies, saying: "The team has looked after me and we're going to have to see going forward. I haven't signed a contract yet, but that's still to be decided in the next week or so, I think."
Kenyan-born Froome had become Cobo's main challenger in the last few days of the three-week race after his Sky team-mate Wiggins had dropped steadily out of contention in the final week.
Wiggins, 31, said: "After everything that's happened it was good but I think in sport you just end up living in the moment.
"I think that when you sit back and look at the season and see what has happened [broken collarbone at the Tour de France], I think you reflect on it with a bit of happiness, but when you finish third, you haven't won and we live for winning unfortunately.
"I'm learning from the disappointments, which is the main thing. Last year was a huge disappointment but we learnt from it and came back stronger."
Froome was unable to overturn his slim deficit in the closing stages before claiming his best ever finish in a Grand Tour, which comprises of the Giro d'Italia, Tour de France and Vuelta a Espana.
Sagan dominated a quality field and held off Italian pair Daniele Bennati and Alessandro Petacchi in Madrid to claim his third Vuelta stage win.
Final stage result:
1. Peter Sagan (Slovakia, Liquigas-Cannondale) 2:20:59secs
2. Daniele Bennati (Italy, Leopard Trek) same time
3. Alessandro Petacchi (Italy, Lampre) same time
12. Bradley Wiggins (Britain, Team Sky) same time
19. Chris Froome (Britain, Team Sky) same time
Overall standings:
1. Juan Jose Cobo (Spain, Geox) 84:59:31secs
2. Chris Froome (Britain, Team Sky) +13secs
3. Bradley Wiggins (Britain, Team Sky) +1:39secs