The Briton finished a close second on the flat 97.8-kilometre stage 1a, just missing out to Vini Zabù sprinter Jakub Mareczko in the dash for the line.
The result is his second podium spot of 2021 after a second place behind Alpecin-Fenix's Tim Merlier at the GP Monseré earlier this month.
Later in the day, after Deceuninck-QuickStep took third on the stage 1b team time trial just two seconds behind winners Israel Start-Up Nation, Cavendish moved up into the race lead – his first leader's jersey since 2017.
"Leading a race for the first time in four years is super nice," Cavendish said after the second half-stage of the day. "With Deceuninck-QuickStep we only have five guys here, so our backs are against the wall a little bit, but they looked after me so well this morning. I'm sorry I couldn't pay them back with a win.
"In the TTT we gave everything, but it'd be nice to wear the leader's jersey for a day and then look forward to supporting Mauri and Mikkel once we get to the climbs."
He'll have another chance to win on Friday's stage 4 in Riccione, while the remainder of the stages see the peloton take on the hills of Emilia-Romagna.
Cavendish's pair of second places so far in 2021 are his best results since 2018, when he took runner-up spots on stages of the Adriatica Ionica Race and Tour of Oman, as well as winning a stage in the Dubai Tour.
He was last in action last week, taking part at Nokere Koerse, where he crashed late on, and the Bredene Koksijde Classic, where he took 30th. He said during the week that he has enjoyed racing in Belgium, calling it "pure, start-to-finish bike racing" and praising the unpredictability of the racing.
Cavendish is expected back in Belgium on April 7 for Scheldeprijs – which he has won three times in the past – while he's currently joined in Italy by Shane Archbold, Mikkel Honoré, Ian Garrison and Mauri Vansevenant. He has also reunited with Danish directeur sportif Brian Holm after his return to Deceuninck-QuickStep.
Check out a clip of the finish of stage 1a of the Settimana Coppi e Bartali below, courtesy of Caja Rural-Seguros RGA, to see how Cavendish and Mareczko match each other in the sprint before the Italian wins it on the line.
🇮🇹 #CoppieBartali Victoria para Jakub Mareczko en el sector inaugural de la primera etapa. @aular_orluis no ha podido pelear en el sprint por una caída en la parte final del recorrido.#SúmateAlVerde 💚 pic.twitter.com/mtOOB0tyWEMarch 23, 2021
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