The Azzurri are the stand-out team in a pool which also contains the Czech Republic, Bulgaria, Armenia and Malta, and will be looking to build on their European Championship performance when they reached the final before losing to Spain.
Italy coach Cesare Prandelli is determined to avoid any over-confidence from his team heading into their World Cup qualifiers, admitting that a 'little fear' among the players usually leads to a better performance.
The Italians are firm favourites to top Group B and go into Friday's opener against Bulgaria in Sofia buoyed by their impressive showing at Euro 2012, where they made it all the way to the final before losing to reigning world and European champions Spain.
However, with the likes of group rivals Czech Republic, Denmark and the Bulgarians unlikely to give Italy a free passage to Brazil 2014, Prandelli knows his side will need to be on their toes.
"The danger is taking success for granted. Instead, we do our best when we have a little 'fear'," said Prandelli.
"Bulgaria are a very good team that is rebuilding, it is relatively young and plays with great determination. They are a very interesting team.
"Tomorrow [Friday] we will face a hostile environment, now we are one of the teams to beat. It will be difficult, but we have trained very well."
Daniele De Rossi looks set to feature following an ankle injury but Mario Balotelli has undergone eye surgery and misses the match while Antonio Cassano has been left out over fitness issues.
Bulgaria's campaign begins with three matches at home - Italy, Armenia on September 11 and Denmark on October 12.
That gives the team the ideal chance to build themselves a platform within the group, according to coach Luboslav Penev.
"We are playing at home early - three matches in fact," he said.
"This is a signal for the crowd to get behind us.
"Those results will be important and we will be chasing a victory in every match."
However, Penev is aware Italy will not be easy opponents - even when Bulgaria have home advantage.
"We're playing one of the strongest teams in the world against Italy," he said.
"At this point, I'm extremely pleased with my players. We're very calm, things are going well. Yes we are outsiders, this is true, But we will try to change that."
Penev had hopes of being able to bring in striker Dimitar Berbatov for the start of their World Cup qualifying campaign, but the new Fulham signing turned down a call-up to the squad.
Denmark midfielder William Kvist has warned Italy they will not have it all their own way in World Cup qualifying group B.
Prandelli has previously said the Czech Republic will be the biggest challenge to his side in the group, but Kvist sees no reason why the Danes cannot pose a threat either.
"Fair enough if Italy think the Czechs are the greatest threat," the Stuttgart player told Ekstra Bladet.
"The Czechs played well at Euro 2012 and it's based on that the Italian coach thinks they have the best momentum right now.
"That's his opinion, but I think we will play some good tight matches against Italy.
"In any case there are four good teams, and Armenia aren't so bad either so I've heard, so it's a very difficult group.
"I don't think Italy have any reason to feel safe because anyone can beat anyone. That could be a positive thing from our point of view."
Czech Republic defender Tomas Sivok also sees Morten Olsen's Denmark as something of a problem, although he is confident they can get a result in Copenhagen this weekend.
"The group is very difficult, but we will not give up hope that we can compete," he said.
"We're not going to Copenhagen on friendly terms. If I did not believe we could get a result I would not be here and instead be spending time with my family.
"I can honestly say that a point for us in Copenhagen would be excellent and a great start to our campaign."
Italy striker Pablo Osvaldo is seeing Friday's trip to Bulgaria as a fresh start to his international career after being overlooked by Prandelli for Euro 2012.
"I didn't do well towards the end of last term and the coach was right not to select me," said the Roma player.
"I had a good pre-season though and I have done well in the league.
"I'll be delighted if I do get a game and I'll give my all, but I'm already happy to just be here again."
Armenia will begin their qualifying campaign with a trip to Malta on Friday.
UEFA World Cup Qualification Group B Fixtures
Malta vs Armenia
Bulgaria vs Italy