Rossi is among four uncapped players picked in the squad alongside Udinese's Simone Pepe and Napoli pair Christian Maggio and Fabiano Santacroce.
There was no place however for veteran Juventus forward Alessandro Del Piero nor the mercurial Antonio Cassano of Sampdoria. Those ommissions are perhaps all the more surprising given the long injury list handicapping Lippi with defenders Marco Materazzi, Nicola Legrottaglie, Marco Cassetti, Fabio Grosso, midfielder Andrea Pirlo and strikers Vincenzo Iaquinta and Marco Borriello all on the sidelines.
It is in the forward positions that Lippi has sprung the biggest surprises with attacking midfielder Maggio and forwards Pepe and Rossi included, while there was also no place for experienced AC Milan midfielder Massimo Ambrosini.
Rossi's inclusion is perhaps less surprising given his great form in Spain over the last year. He scored 11 goals in 23 league matches for Villarreal last season and has already hit the mark this season with one goal in two games after an injury interrupted start to the campaign.
Defending champions Italy top Group 8 after winning their first two qualifiers against Cyprus and Georgia and play away to Bulgaria on 11 October and host Montenegro on 15 October.
Goalkeepers: Gianluigi Buffon (Juventus), Marco Amelia (Palermo), Morgan De Sanctis (Galatasaray/TUR)
Defenders: Daniele Bonera (AC Milan), Fabio Cannavaro (Real Madrid/ESP), Giorogio Chiellini (Juventus), Andrea Dossena (Liverpool/ENG), Alessandro Gamberini (Fiorentina), Fabiano Santacroce (Napoli), Gianluca Zambrotta (AC Milan)
Midfielders: Alberto Aquilani (AS Roma), Mauro Camoranesi (Juventus), Daniele De Rossi (AS Roma), Gennaro Gattuso (AC Milan), Christian Maggio (Napoli), Ricardo Montolivo (Fiorentina), Antonio Nocerino (Palermo), Simone Perrotta (AS Roma)
Forwards: Antonio Di Natale (Udinese), Alberto Gilardino (Fiorentina), Simone Pepe (Udinese), Giuseppe Rossi (Villarreal/ESP), Luca Toni (Bayern Munich/GER)