The France international, who arrived at Bernabeu this summer on a free transfer from Paris Saint-Germain, is yet to feature for Los Blancos, having been given an extended break following Euro 2024.
Mbappe has had less than a week of training with his new club, but the attacker has been named in Carlo Ancelotti's first XI for the UEFA Super Cup against the Europa League holders.
Rodrygo, Jude Bellingham and Vinicius Junior also start in a star-studded attack, while Federico Valverde and Aurelien Tchouameni will operate as the midfield two, with Eduardo Camavinga out injured.
Mbappe to make Real Madrid debut against Atalanta
Dani Carvajal captains the team from right-back, while Eder Militao starts in the middle of the defence, with the Brazilian looking to put his injury problems from last term behind him.
As for Atalanta, there is not a recognised number nine in their side, with Ademola Lookman being joined by Charles De Ketelaere in the final third.
Mario Pasalic will be the most advanced of the midfielders, while there is a spot in the middle for Ederson, who is currently being linked with the likes of Manchester United.
New signing Mateo Retegui is on the bench, but there will be an official debut for De Ketelaere, with the 23-year-old moving to the club on a permanent basis from AC Milan following a successful loan spell.
Real Madrid: Courtois; Carvajal, Militao, Rudiger, Mendy; Valverde, Tchouameni; Rodrygo, Bellingham, Vinicius; Mbappe
Subs: Lunin, Gonzalez, Modric, Guler, Endrick, Vazquez, Vallejo, Ceballos, F Garcia, Brahim, Ramon
Atalanta BC: Musso; Djimsiti, Hien, Kolasinac; Zappacosta, De Roon, Ederson, Ruggeri; Pasalic; De Ketelaere, Lookman
Subs: Carnesecchi, Rossi, Godfrey, Sulemana, Bakker, Cassa, Retegui, Comi, Tornaghi, Manzoni, Vavassori