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A 10-woman breakaway battled for the win in the final 10 kilometres of the 102 km stage in Walsall but it was Pieters (SD Worx) who kept her composure to claim victory.
France’s Copponi (FDJ Nouvelle-Aquitaine Futuroscope) was pipped to the line by Pieters but took the general classification lead after finishing third on Monday’s opening stage.
The win was Pieters fourth career Women’s Tour stage win and moves her to second overall in the general classification.
“It was a hectic final,” Pieters said after her dramatic win.
“I think the whole day was pretty hectic. There was still a small gap after the last corner but I thought I just need to start to sprint. It was an urgent sprint but it went well in the end.
“The whole day was really aggressive, I think that we were the only ones attacking. We kept attacking with the team and at the end we went away and it was a really good group and luckily we made it.”
Overnight race leader Marta Bastianelli (Alé BTC Ljubljana) finished within the peloton, 46 seconds behind the leaders, and conceded the blue jersey to Copponi, who is making her debut in the race in 2021.
Copponi and Pieters are level on time, while only six others are within 10 seconds of the race lead going into Wednesday’s individual time trial in Atherstone, North Warwickshire.
Trek-Segafredo’s Chloe Hosking was the best of the Australian riders finishing in 12th, while fellow Aussie Sarah Roy (Team BikeExchange) came home in 26th place 2 minutes and 38 seconds behind the winner.
After setting off from Walsall’s Victorian Arboretum in wet conditions the peloton tackled 10 laps of a 10-kilometre circuit featuring the climb of Barr Beacon each time around.
The penultimate lap brought multiple attacks, with the race-winning move going clear and building a lead of half a minute on the run back to the finish in Walsall town centre.
British rider Pfeiffer Georgi (Team DSM) went clear in the last kilometre, leading through the final turn on to the Lichfield Street finishing straight, but with only a handful of metres’ of advantage over the fast-charging Pieters and Copponi who powered home to take the win.
The Women’s Tour heads to North Warwickshire for Stage three and the event’s first-ever individual time trial.
The route is a 16.6-kilometre course that starts and finishes in the Atherstone Town centre.