The Italians host Gareth Southgate's side in Naples, and the game will be their first since ex-striker and coach Vialli died in January.
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Vialli earned 59 senior caps and worked as an assistant to Mancini as the Azzurri lifted the European Championship trophy with victory over England at Wembley in 2021.
Italy will wear one-off shirts carrying the message 'Luca, forever an Azzurro' inside the collar in honour of Vialli.
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Mancini hailed the former Chelsea forward and manager on the eve of the game in Naples.
"It is very emotional obviously," he said.
"It is the first time we have played a game since Luca's passing.
"We were very fortunate to have him, me as a team-mate and to work alongside him, you were lucky enough to have him in London and he had almost become an honorary Londoner, so you saw what he was all about.
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"It is with a great sadness but people like him will always be close to us, he is immortal and will stay close to us."
Italy and England have become familiar foes in recent years, having also faced off in the most recent Nations League campaign on the back off Mancini's side's penalty shootout win in the Euros final.
"It has become a bit of a clasico, Italy versus England," Mancini said.
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"It is the fourth time we have played them in two years, England are one of the best sides in the world, have an extraordinary squad available for selection, they have always been very unlucky and I think it will be a very tough match tomorrow night.
"We went from a triumph to a huge disappointment. Winning the Euros then not qualifying for the World Cup. Football can be cruel, I don't think the team deserved that.
"We qualified for the Nations League finals twice, it's important. We can't say we've been less good, we were unfortunate."
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"Of course we made mistakes and we need to start again with the same targets in mind."