Securing the individual time trial title on Thursday (AEST), van der Breggen became just the second woman in history since French rider Jeannie Longo (1995) to achieve the double-rainbow feat after the introduction of the race against the clock to the world championships in 1994.
The Dutchwoman leapt away on the penultimate ascent of the steep Cima Gallisterna 41kms from the finish, leaving behind a bunch already destroyed by the work of her team mates Marianne Vos and broken wristed Annemiek van Vleuten on the climb.
"Incredible," 30-year-old van der Breggen said. "It was a really hard race. Fighting from the beginning.
"The climbs were really really tough. In the third lap I felt strong and we discussed in front we tried to make the race hard and we did.
"I just went for it."
"I thought in the last lap everybody's tired it's difficult to make the difference maybe on the climb, I felt good so i went but it was really far.
The 2016 Olympic champion adds another rainbow jersey to her heaving palmarès after she won at Innsbruck, Austria in 2018, the Netherlands' fourth consecutive women's road race title.
Despite the post-race interviewer drawing comparisons to that victory, van der Breggen was having none of it.
"This circuit was different to Innsbruck. It had some flat parts but it was hard all the time.
"I'm really happy. i never expected this. We expected a hard race but it's incredible."
The normally composed five-time winner of Flèche Wallonne teared up on the podium perhaps reflecting on her looming retirement after the 2021 season and her stellar year so far - double rainbows and early September's Giro Rosa title.
"I'm pretty tired now this season is pretty good so far."
Elisa Longo Borghini (ITA) and Annemiek van Vleuten (NED) fought for the podium scraps after they escaped from the remnants of bunch on the final climb, the Italian appearing to bump shoulders in frustration with the 2019 world champion who had her number.
The Netherlands set the pace hard early on as a number of riders were dropped early. But Van der Breggen was caught up in a small tangle 120kms from the finish and took some kilometres to get back on with the help of several team mates.
The peloton didn't respond and applied no pressure back up the front, quite possibly missing an opportunity, happy to let the inevitable catch happen.
Solo early attacks from Valerie Demey (BEL) 107kms from the finish and Alison Jackson (CAN) at 93kms to go were easily absorbed by the peloton until Australia's Grace Brown used a dangling Jackson to launch a raid on the Imola race track with 88kms to go.
Their attack enticed across Tayler Wiles (USA), Alice and Hannah Barnes (GBR), Lisa Brennauer (GER), Susanne Andersen (NOR), Amy Pieters (NED), Katia Ragusa (ITA), Juliette Labous (FRA) and Christine Majerus (LUX) as the road went upwards again up the Mazzolano.
Not wanting to miss out, Mavi García (ESP) counterreacted and made it across on the climb. A few kilometres later, Brown was distanced and fell back to the bunch, the leaders soon losing Alice Barnes the third time up the Cima Gaillsterna as they held a minute and half advantage.
When the leaders hit 66kms to go, Eugenia Bujak (SLO) escaped in an ultimately fruitless attempt to join the leaders who themselves were caught with 42kms to go as the Dutch put the hammer down, van Vleuten splitting up the bunch, van der Breggen escaping down the left hand side.
Only Borghini, Ludwig and Deignan could rally behind van Vleuten as van der Breggen never looked back.
Australia's best placed rider was Lucy Kennedy in 28th.
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