The coach had previously called up Brazil-born striker Amauri and Argentina-born midfielder Cristian Ledesma and although neither feature in this squad, it has not put Prandelli off causing a new stir among fiercely patriotic Italian pundits.
Ex-Barcelona midfielder Thiago Motta played for Brazil in the 2003 CONCACAF Gold Cup when an Under-23 team were invited.
An Italian federation statement said the 28-year-old's callup was still "subject to formal authorisation by FIFA".
On-loan Juventus forward Alessandro Matri, who scored two goals against parent club Cagliari in Saturday's 3-1 win and in-form Parma winger Sebastian Giovinco, on-loan from Juve, also received first call-ups for Wednesday's game in Dortmund.
Goalkeeper Gianluigi Buffon is back for the first time since coming off in Italy's first game at the World Cup and having back surgery but others like striker Mario Balotelli are out injured.
AC Milan forward Antonio Cassano has also returned to the squad after missing November's 1-1 friendly draw with Romania after being dropped by former club Sampdoria in an internal row.
