Vollering came to the final few hundred metres in a group of five riders, led-out by teammate and reigning world champion Anna van der Breggen. Annemiek van Vleuten (Movistar) launched first along the barriers, but it was the rapid Vollering who followed the acceleration then sprinted around van Vleuten to complete the biggest win of her career.
"Amazing. Anna did such a great job and the whole team.. that I could finish it off... it's awesome," said an emotional Vollering. "I'm really grateful that they did it for me, they're such a great team."
Vollering had latched onto the top climbers of the race over the top of the Roche-aux-Fachons, where the final selection was made during a van der Breggen surge from the base to near the top of the decisive final climb.
"It was really hard on the climbs, at one moment, we were with this group that we finished with and then Vos was back," said Vollering. "It's better to not sprint with her of course. A little break again and Anna did the lead-out the last 10 kilometres or something, it was awesome. I'm really happy!"
Van Vleuten was a tenacious second, with Elisa Longo Borghini (Trek-Segafredo) third and re-taking the lead in UCI Women's WorldTour standings.
Earlier in the race, it was a relatively sedate start to the race, a departure from the hot starts in recent classics in the Ardennes.
Claire Faber (Andy Schleck-CP NVST-Immo Losch) and Silvia Zanardi (Bepink) were the closest thing to an early break, but they were given very little leeway by the peloton and only got a gap of three minutes before the main bunch began chasing them back.
They were caught at the top of the first climb of the day, the Côte de Wanne, with a solo attack from Niamh Fisher-Black (Jumbo-Visma) going free over the top.
The young New Zealander made a lonely figure off the front of the race until an attacking group from the peloton of Tayler Wiles (Trek-Segafredo), Lucy Kennedy (Team BikeExchange), Anouska Koster (Jumbo-Visma), Elise Chabbey (Canyon-SRAM), Leah Thomas (Movistar), and Brodie Chapman (FDJ Nouvelle Aquitaine Futuroscope) made their way to join Fisher-Black.
The group weren't the most cooperative and were also hampered by a crash to Kennedy, with the Australian crashing just before the group was recaught on Cote de Desne with 47 kilometres to go.
Fisher-Black continued her determination to attack, jumping away solo just after the crest of the climb. She grew her lead out to 30 seconds, but as the teams positioned their star climbers into the foot of the Cote de la Redoute, the New Zealander was caught.
The signature climb of the race proved the spot for Ashleigh Moolman (SD Worx) to attack, initially followed by Marta Cavalli (FDJ Nouvelle Aquitaine Futuroscope) and Thomas before the South African kicked clear to lead solo until the fireworks began behind.
Cecilie Uttrup Ludwig (FDJ Nouvelle Aquitaine Futuroscope) attacked up to Moolman, with the top climbers of the women's peloton stretching themselves to follow the powerful Dane's move.
Over the top of the climb there were just a group of 12 or so riders in contention, but Lucinda Brand (Trek-Segafredo), Uttrup Ludwig and Moolman jumped clear and made a dangerous looking break as the road flattened out.
The trio got a decent gap of 25 seconds quite quickly, but as the chasing bunch swelled behind in the run to the Cote des Forges, some lack of cooperation showed as Moolman began to skip turns. The gap increased back out to 30 seconds over the climb as the peloton opted to keep together and maintain their domestiques on the run into the finale.
The trio were caught as the pace ramped up into the base of the Roche aux Fachons, as the top riders tried to get into the foot of the climb in good position.
Van der Breggen led the way from the base to the top of the steep climb, eliminating most of the remaining riders and slimming down the front group to just Longo Borghni, Vollering, Van Vleuten, Moolman and Kasia Niewiadoma (Canyon-SRAM). Marianne Vos (Jumbo-Visma) and Uttrup Ludwig worked hard after the summit of the climb and managed to return to the front group, but another attack, this time from van Vleuten slimmed it down to a front group of just five riders, dropping Vos, Moolman and Uttrup Ludwig.
From there, van der Breggen went to the front to assume control of the race for teammate Vollering, who possesses a very good sprint. The world champion looked for no help as she led all the way into the finish, keeping the Vos group at bay and allowing Vollering to take the biggest race of her career.