Vialli, who featured at the 1986 and 1990 World Cup finals, spent a significant period of his football career in England, playing for and coaching Chelsea between 1996 and 2000, before also managing Watford during the 2001-2002 season.
England will meet Italy in their Group D opener in Manaus on Saturday and Vialli is confident that his nation will finish ahead of Roy Hodgson's men, as Uruguay and Costa Rica also eye one of the two qualification places.
Vialli is convinced that England will struggle to cope with the pressure put on them by expectant supporters, while the 49-year-old does not think the issue will be a problem for Italy's players, who he claims "eat pressure for breakfast".
He told Perform: "I think it's quite funny with England because for about four years all the England fans and the England players feel a bit depressed and disillusioned when it comes to the England side.
"And then one month before the World Cup starts everybody sort of starts feeling that they (will) naturally win it and everybody feels super-confident. I think that England fans should try to find a balance in between both state of minds.
"But I think the England players find it quite difficult when they play in the World Cup because they are not used to the pressure. When they play in the Premiership (Premier League), when they play Manchester United versus Chelsea for example or Arsenal, there's no pressure, it's actually quite fun to play.
"You know that there are no consequences if you don't do well as long as you do your best on the pitch. And therefore, when they play for the national team, when they wear the England shirt, all of a sudden they realise they are representing their country, they feel there is a massive expectation, there's a lot of scrutiny and a lot of consequences.
"It's the inability to handle the pressure that makes a big difference between between the Italian players and the England players when it comes to the World Cup stage.
"The Italian players, they eat pressure for breakfast, so they grow up with a lot of pressure and they know how to handle it. Also we (Italy) are very good at winning games even though we are not playing at our best, which is something that England players need to learn quite fast if they want to succeed in the World Cup, because there will be one or two games where you will not be performing so you need to be able to win it anyway.
"We are good at that, historically we are very good at that."
Although Vialli is not convinced by England's ability to perform under intense pressure, he acknowledges they are more than capable of posing a threat on Saturday.
"I think England are a very exciting side because they have got so many young, talented, creative players, playing up front," he added.
"The likes of (Daniel) Sturridge, (Wayne) Rooney, and (Raheem) Sterling, (Adam) Lallana, (Danny) Welbeck, they can turn hot quickly and can create problems for the opposition.
"They need to be a bit more clinical, though, because there won't be many goal-scoring opportunities, so they need to take their chances when they can."
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