Cesare Prandelli's already qualified side put in a disappointing performance against Denmark on Friday but will be hoping to make amends in Naples.
Armenia plays its final World Cup qualifier with a chance of making the playoffs, but faces a tough trip to Group B winner Italy.
Vardan Minasyan's side is fifth in the pool but trails second-placed Bulgaria by just one point, meaning the team could still finish immediately behind Cesare Prandelli's men.
The scenario is unlikely as it would require Bulgaria and the Czech Republic to draw - with Denmark also failing to beat bottom-placed Malta - while Armenia wins in Naples to secure one of the eight best runner-up spots.
Armenia has been inconsistent throughout its qualifying campaign, winning four but losing five of its nine fixtures, but a 2-1 home victory over Bulgaria on Friday ensured the side kept its hopes of reaching Brazil 2014 alive.
In terms of team news, Spartak Moscow forward Yura Movsisyan is set to lead the line for Armenia.
The 26-year-old has three goals in qualifying so far, and will look to provide the attacking threat in Tuesday's fixture, while Borussia Dortmund playmaker Henrikh Mkhitaryan is also likely to start.
Italy, which won the 2006 World Cup, has enjoyed a comfortable campaign in Group B, winning six and drawing three of nine games to secure automatic qualification.
Milan striker Mario Balotelli - who missed the 2-2 draw with Denmark on Friday - has remained with the squad despite suffering from gastroenteritis.
Meanwhile, Southampton forward Pablo Osvaldo is likely to once again start up front and will look to add to the goal he scored against Morten Olsen's outfit.
Italy is looking for a second qualification win over Armenia, after triumphing 3-1 in the away encounter in Oct. 2012.
Goals from Andrea Pirlo, Daniele De Rossi and Osvaldo were enough for them to claim maximum points in Yerevan.