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Vollering attacked from a group of pre-race favourites before the final gravel sector of the course and managed to dodge a runaway horse en route to the finish line where her and Kopecky did battle.
So tight was the finish that Vollering only learned she had won while being interviewed by a reporter afterwards, Kopecky following up last year's win with a second place and Kristen Faulkner (Team Jayco-AlUla) claiming the last podium place after a solo attack with 32 kilometres to go that was only bested by the star SD Worx pair.
Vollering was full of praise for her teammates and discussed the memorable duel with Kopecky in the post-race interview.
“It was a crazy final," Vollering said after the finish.
"We did very well as a team, the other girls rode super strong today and did everything, Mischa [Bredewold], Niamh [Fisher-Black], Anna Shackley, Elena [Cecchini], they all did a super good job and then the final playing with Lotte was really cool.
"I attacked and felt like ‘this is the moment’ and just went how we discussed because this was the plan, too. Then, suddenly, Lotte was with me, and that was very nice, it’s just teammates together and then you can also go a bit deeper together.
“I always really, really liked this race but always worked for my teammates here. It was also always very early always for me, and I didn’t have so strong belief in myself yet."
The nervy first half of the 136 kilometre race saw few attacks as the peloton rode conservatively, a breakaway of four getting off the front briefly through the fourth gravel sector before being reeled in on the fifth and longest sector as riders prepared for the finale.
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Karlijn Swinkels (Team Jumbo-Visma) attacked with 47 kilometres to go with Faulkner joining her shortly after, and the duo carved out a gap of as much as 1 minute and 30 seconds on the peloton.
Faulkner took her chance and went solo on a short climb with 32 kilometres to go, leaving Swinkels behind. The American looked to have serious power and held a gap of 1 minute and 46 seconds at the start of the Colle Pinzuto, when the favourites took up the challenge in the peloton behind.
Annemiek van Vleuten (Movistar) accelerated to pull away and was joined by Cecilie Uttrup Ludwig (FDJ-SUEZ), Puck Pieterse (Fenix-Deceuninck), Liane Lippert (Movistar Team), Katarzyna Niewiadoma (Canyon-SRAM), Vollering and Kopecky to make up the group to catch Faulkner.
Vollering quickly attacked from the chasing group, building a sizeable gap before a horse ran onto the road in front of her as she was forced to brake to avoid scaring it further. Eventually, the horse fell going through a corner, and Vollering continued to hunt down Faulkner, bringing the gap down to 59 seconds at the start of the final gravel sector, Le Tolfe.
It was on the brutally steep Le Tolfe climb that Kopecky attacked and bridged to Vollering, the SD Worx duo steadily slimming down Faulkner's advantage before catching her inside the final two kilometres on the Via Santa Caterina.
Vollering came together with Faulkner as she tried to pass the Jayco-AlUla rider, then recovered to accelerate and lead by the top of the climb into Siena. She led the way, until Kopecky shot ahead into the final corner. The two came back together for the final sprint and it was the Dutchwoman who came with late speed to beat her Belgian teammate.
