De Rossi trained as part of three-man defence as Italy head coach Cesare Prandelli tested a 3-5-2 formation ahead of the Group B leaders' World Cup qualifier on Tuesday against the Czechs at Juventus Stadium in Turin.
While De Rossi has spent most of his career as a defensive midfielder, the 30-year-old did play as part of a back four for Italy in their friendly versus Argentina last month and with full-backs Ignazio Abate and Luca Antonelli out injured, Maggio said he believes Prandelli's experiment may work.
"De Rossi has already played a few matches as centre-back and he hasn't made a bad performance at all," Maggio said on Sunday.
"Of course he isn't a defender but his great technical skills allow him to cover that role."
If De Rossi is picked in defence, he is expected to play in the centre of the back three with Napoli's Maggio and Emanuele Giaccherini of Sunderland set to start out as wing-backs.
Italy can secure a berth at next year's World Cup finals in Brazil if they overcome Czech Republic.
Juventus defender Leonardo Bonucci, who will most likely play alongside De Rossi, cannot wait to represent his country at his home stadium and, potentially, lock up a spot for the finals in Brazil next year.
Tuesday's World Cup qualifier will be the first international played by Italy at Juventus Stadium.
"Every time you enter the pitch in an Italian shirt, you feel a very deep emotion and a willingness to give something more," Bonucci said.
"To play in this stadium wearing the national team's jersey is even more exciting because we'll be the first and we hope we'll inaugurate it in the best possible way."
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