The Dutch face Mexico in a friendly on November 12 before attempting to resurrect their flagging Euro 2016 qualifying campaign at home to Latvia five days later.
And coach Guus Hiddink has brought the two defenders from the international wilderness as he looks to freshen up his squad.
PSV's Willems has not featured for the national side since a 2-2 draw with Japan last November, but is included after impressing in the Eredivisie.
Van Rhijn of Ajax, meanwhile, has also won a call-up having been out of international action since August 2013.
Jeremain Lens, Daryl Janmaat and Jeffrey Bruma are among the highest-profile players to have missed out on inclusion in the 26-man party
Netherlands currently sit third in Group A having won just one of their opening three Euro 2016 qualifiers.
Squad in full:
Goalkeepers: Jasper Cillessen (Ajax), Tim Krul (Newcastle United), Kenneth Vermeer (Feyenoord), Jeroen Zoet (PSV).
Defenders: Daley Blind (Manchester United), Virgil van Dijk (Celtic), Bruno Martins Indi (Porto), Ricardo van Rhijn (Ajax), Joel Veltman (Ajax), Paul Verhaegh (Augsburg), Ron Vlaar (Aston Villa), Stefan de Vrij (Lazio), Gregory van der Wiel (Paris Saint-Germain), Jetro Willems (PSV).
Midfielders: Ibrahim Afellay (Olympiacos), Jordy Clasie (Feyenoord), Nigel de Jong (AC Milan), Memphis Depay (PSV), Leroy Fer (QPR), Davy Klaassen (Ajax), Luciano Narsingh (PSV), Quincy Promes (Spartak Moscow), Arjen Robben (Bayern Munich), Wesley Sneijder (Galatasaray).
Forwards: Klaas-Jan Huntelaar (Schalke), Robin van Persie (Manchester United).
