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.
However, this has been deemed not to count as full international level so he has been able to be called up by Italy thanks to an Italian grandfather giving him dual nationality.
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.
Italy, who top Euro 2012 Group C and next visit Slovenia in a qualifier on March 25, met Germany in Dortmund for the 2006 World Cup semi-final before going on to win the trophy.
Squad:
Goalkeepers: Gianluigi Buffon (Juventus), Salvatore Sirigu (Palermo), Emiliano Viviano (Bologna)
Defenders: Davide Astori (Cagliari), Leonardo Bonucci (Juventus), Mattia Cassani (Palermo), Domenico Criscito (Genoa), Giorgio Chiellini (Juventus), Christian Maggio (Napoli), Andrea Ranocchia (Inter Milan)
Midfielders: Alberto Aquilani (Juventus), Daniele De Rossi (AS Roma), Sebastian Giovinco (Parma), Stefano Mauri (Lazio), Riccardo Montolivo (Fiorentina), Thiago Motta (Inter), Antonio Nocerino (Palermo), Angelo Palombo (Sampdoria)
Forwards: Marco Borriello (Roma), Antonio Cassano (AC Milan), Alessandro Matri (Juventus), Giampaolo Pazzini (Inter), Giuseppe Rossi (Villarreal)
