The 47-year-old referenced the Azzurri's imperious form over their rivals but believes that the tough Brazilian conditions will affect the outcome of their World Cup group clash
The tournament draw, which took place on Friday, saw the European pair pitted against each other in Group D alongside Uruguay and Costa Rica.
England have won their last two friendly encounters with the Azzurri, both in 2-1 scorelines, but lost on penalties in their Euro 2012 quarter-final clash and the Chelsea legend is confident that Roy Hodgson's men are the underdogs.
"At this moment, Italy are the favourites," he told La Gazzetta dello Sport. "In major tournaments we have beaten England in 1980, 1990 and 2012.
"The English tend to beat us in friendlies, such as in August 2012, but in official competition they struggle. I don't know why that is but perhaps Italy are more prepared for facing a World Cup, while the English are exhausted at the end of the season. Their fixture list is non-stop."
Considering how the Three Lions might be exploited, the former Italy international observed: "The weaknesses are the goalkeeper and defence in general. Joe Hart is having a difficult time, while losing charismatic figures like John Terry and Rio Ferdinand weakened the back four.
"The replacements have not shown themselves to be up to the task, so our strikers could really make the difference.
"England's hope is that some young players can make their mark leading up to the World Cup. Jack Wilshere or Ross Barkley seem ready, in my view. However, Italy have something more."
Zola also believes that the hot and humid conditions in the Amazonian climate will play a big part in determining the course of the match.
"The game that can set the tone for a tournament is usually the opener, so in this case I think Italy-England will fit the bill," he added.
"Along with the technical difficulties of two football powers, the climactic conditions will add to the problems. Manaus is hot, humid and far away. The English fear having to play there but it won't be easy for us Italians either, so physical fitness will be fundamental."