Evenepoel let out a roar as he crossed the line two seconds ahead of his general classification rival, leaving the pair tied on time ahead of Giulio Ciccone (Trek-Segafredo) who also finished third on the day.
Roglic remains the overall leader as the seven-stage race enters its halfway mark, though the momentum is now with his Soudal Quick-Step rival after a blistering turn of pace on the final left-hand bend made the difference.
“I felt better and I had a lot of confidence in my team that they could do the job they did,” Evenepoel said after the race.
“The climb before La Molina was a long one and a tough one, and we wanted to make it as hard as possible from that climb on, and it paid off.”
“I showed already in the first days I’m quite fast. On the first day (when Roglic won), I made a mistake because I was too far back when I started the sprint. But now we seen today that I’m fast here as well.”
In what was the only full day in the Pyrenees at this year’s Volta, the first break of the stage got off to a fast start and featured the likes of Richard Carapaz (EF Education-EasyPost), Guillaume Martin (Cofidis), Simone Petilli (Intermarche-Circus-Wanty), Filippo Zana (Jayco AlUla), Maxim van Gils (Lotto-Dstny), Niklas Eg (Uno-X Pro Cycling) and Jefferson Cepeda (Caja Rural-Seguros RGA).
Petilli was the first to take charge on the first ascent of the 180.5-kilometre stage, the Coubet, and took maximum points for the mountains classification, before the seven-strong group tackled all 18 kilometres worth of the Coll de la Creueta.
At that stage the peloton trailed by almost five minutes, a gap which slowly reduced when Pieter Serry, Evenepoel and their five Soudal Quick-Step teammates took charge from the front.
The decision to chase on the Creueta doubled as an attempt to isolate Jumbo-Visma star Roglic, who only had Sepp Kuss and Steven Kruijswijk to count on for the remaining eight kilometres to the summit.
Martin led the four-man breakaway up over the summit and by then the peloton had been reduced to 40 – Cepeda and Ineos Grenadiers duo Geraint Thomas and Egan Bernal among those to have lost contact.
As the final ascent approached, the gap had dropped to within a minute and allowed Ilan van Wilder to stretch out the bunch for leader Evenepoel’s ensuing surge.
Carapaz was the first to increase the pace inside the final 10 kilometres, but once the Olympic champion gave way, van Wilder set things up for his compatriot to attack in the final kilometres.
Roglic responded almost instantly; the pair creating a 15-second advantage en route to one final duel that was ultimately won by the world champion.
With Ciccone crossing 13 seconds later in third, Jai Hindley (Bora-Hansgrohe) was next over the line along with Joao Almeida (UAE Team Emirates) and the remaining GC contenders.
Stage 4 will see the peloton travel 188 kilometres to Sabadell, and SBS VICELAND and SBS On Demand will have all the action from 1:30am (AEDT) on Friday, March 24.
