Canadian-born De Guzman, who scored twice in Swansea's 3-1 win over Stoke at the weekend, has been eligible for selection by the Oranje since earning Dutch citizenship in 2008 but has so far been overlooked despite impressive spells at Feyenoord, Real Mallorca and Villarreal.
De Guzman has now caught the eye of Holland coach Louis van Gaal having turned in a series of strong performances since arriving at Swansea in the summer on a season-long loan from Villarreal.
Benfica winger Ola John and Ajax defender Daley Blind could join De Guzman in making their debuts against the Italians at the Amsterdam ArenA on February 6 after also earning places in the initial 23-man squad, which will be finalised on February 1.
There was no place in the squad for captain Wesley Sneijder, who this week completed a protracted transfer to Galatasaray, while Hamburg's Rafael Van der Vaart, John Heitinga of Everton and Arjen Robben of Bayern Munich were also absent.
FC Twente's Brazilian-born defender Douglas was another player to miss out despite earning his first call-up to the squad in October after being granted Dutch nationality.
Squad: Krul (Newcastle), Vermeer (Ajax), Vorm (Swansea); Blind (Ajax), Boulahrouz (Sporting Lisbon), Janmaat (Feyenoord), Mathijsen (Feyenoord), Martins Indi (Feyenoord), Van Rhijn (Ajax) De Vrij (Feyenoord); Clasie (Feyenoord), Fer (FC Twente), Van Ginkel (Vitesse Arnhem), De Guzman (Swansea), Maher (AZ Alkmaar), Strootman (PSV Eindhoven); Huntelaar (Schalke), John (Benfica), Kuyt (Fenerbahce), Lens (PSV Eindhoven), Van Persie (Manchester United), Chess (Feyenoord), Van Wolfswinkel (Sporting Lisbon).