The 2019 World Champion was forced to start his sprint early to close down a long-range attack from eventual third-placed Pascal Ackermann (UAE Team Emirates) and had enough in the legs to edge out Bryan Coquard (Cofidis) who finished second.
The win marks Pedersen's first at La Vuelta and second at Grand Tours this season after also taking out Stage 13 at the Tour de France in July. The Dane has the points classification essentially won with 247 points, 151 ahead of closest challenger Marc Soler (UAE Team Emirates) with 8 stages to go.
"We knew that the final was super good, so the boys did really good and everyone was super focused the whole day," Pedersen said after the stage.
"I'm just happy I can finally get the win and give the boys back all the work they've done so far, it's really nice for all of us.
"We came here for a stage win and we have one, so now we keep fighting to get one more. It's super nice to have the lead in the points jersey.
Attacks flew from the very start of the 163 kilometre stage, as a three-man break went up the road with Julius van den Berg (EF Education-EasyPost), Ander Okamika (Burgos-BH), and Joan Bou (Euskaltel-Euskadi).
Trek-Segafredo, BikeExchange-Jayco, and Cofidis all took turns on the front of the peloton to keep the trio on a tight leash, the gap never going above 4 minutes as they traversed the rolling hills.
Van den Berg was the first to be swallowed up as his compatriots followed moments later and the peloton was all together with 10 kilometres to go, riders taking up formation for what would be a sprint finish.
Jumbo-Visma led the bunch into the flamme rouge before Ackermann launched with 300 metres to the line in a surprise attack and Pedersen went in pursuit, catching the German with 150 metres to spare as Coquard was the best of the other sprinters to take second.
There was predictably no action in the general classification, Remco Evenepoel (QuickStep AlphaVinyl) protecting the red jersey as he came in with the bunch.
The Vuelta a Espana returns to the mountains in Stage 14 with a 160 kilometre course from Montoro to a brutal double climb finish culminating at the summit of the Sierra de la Pandera. Watch the action from 10:50pm (AEST) LIVE on SBS and SBS On Demand.
