The double-header holds no meaning for Cesare Prandelli's men, who booked their place at the Brazil finals with two games to spare, but the games offer Rossi a first appearance in Azzurro colours since October 2011.
The 26-year-old has marked his return from a lengthy lay-off with cruciate ligament damage by firing six goals in seven games for Fiorentina this season and the former Italy captain could add to his six-goal haul for his country over the international break.
Roma full-back Federico Balzaretti returns to the squad - which meets Denmark in Copenhagen on October 11 before hosting Armenia in Palermo four days later - for the first time since November 2012. The 31-year-old has played a key role in Roma's unexpected seven-game winning run from the start of the Serie A season.
Sunderland winger Emanuele Giaccherini, Southampton striker Dani Osvaldo and the Paris St Germain trio of Salvatore Sirigu, Marco Verratti and Thiago Motta must travel home to Italy and Coverciano for the training camp that precedes Thursday's trip to Denmark.
Mario Balotelli is included alongside fellow strikers Alessio Cerci, Federico Insigne, Osvaldo and Rossi despite earning a three-match ban for insulting the referee in AC Milan's recent defeat to Napoli. Prandelli has typically excluded players suspended from domestic competition for violent or aggressive conduct.
Juventus goalkeeper Gianluigi Buffon is retained and will pass Fabio Cannavaro's all-time appearance record should he earn a 137th cap in either match.
Italy squad: Buffon (Juventus), Marchetti (Lazio), Sirigu (Paris St Germain); Abate, Astori (Cagliari), Balzaretti (Roma), Bonucci (Juventus), Chiellini (Juventus), De Silvestri (Sampdoria), Pasqual (Fiorentina), Ranocchia (Inter Milan); Aquilani (Fiorentina), Candreva (Lazio), De Rossi (Roma), Diamanti (Bologna), Florenzi (Roma), Giaccherini (Sunderland), Marchisio (Juventus), Montolivo, Pirlo (Juventus), Poli, Thiago Motta (Paris St Germain), Verratti (Paris St Germain); Balotelli, Cerci (Torino), Gilardino (Genoa), Insigne (Napoli), Osvaldo (Southampton), Rossi (Fiorentina).