The 21-year-old defender joined the Citizens from RB Leipzig for around £77.6m earlier this summer and made his debut as a substitute in the 3-0 Premier League win over Burnley last Friday.
Pep Guardiola has now decided to hand the Croatian his full debut in this evening's UEFA Super Cup contest along with compatriot Mateo Kovacic, who joined from Chelsea last month.
Guardiola has made a total of four changes to the side that beat Burnley, with Gvardiol, Kovacic, Cole Palmer and Jack Grealish all handed starts at the expense of Rico Lewis, Julian Alvarez, Bernardo Silva and Kevin De Bruyne, the latter of whom reaggravated a hamstring injury against the Clarets and is facing up to four months on the sidelines.
Gvardiol will be joined in a back four with captain Kyle Walker, Manuel Akanji and Nathan Ake, while Rodri and Kovacic will operate in centre-midfield in front attacking quartet Palmer, Grealish, Phil Foden and Erling Haaland, who netted a brace against Burnley.
Bernardo is unavailable for selection due to illness, while Ruben Dias has been named on the substitutes' bench despite sustaining a concussion in training last week.
As for Sevilla, Jose Luis Mendilibar has made two changes to the side that lost 2-1 against Valencia in La Liga last weekend, with Joan Jordan and Oliver Torres starting at the expense of Suso and former Man City man Fernando.
Another ex-Citizens player Jesus Navas does start, though, and is set to captain the side at right-back, joining Loic Bade - who was sent off on his Sevilla debut against Valencia - Nemanja Gudelj and Marcos Acuna in the back four.
Ivan Rakitic will operate in centre-midfield with Jordan and Torres, while Youssef En-Nesyri leads the line in between wingers Erik Lamela and Lucas Ocampos.
After lifting their first-ever Champions League trophy last season, Man City are competing in the UEFA Super Cup for the first time against a Sevilla side who won a record-extending seventh Europa League title in 2022-23.
Manchester City lineup: Ederson; Walker, Akanji, Gvardiol, Ake; Rodri, Kovacic; Foden, Palmer, Grealish; Haaland
Subs: Ortega, Carson, Dias, Phillips, Stones, Laporte, Alvarez, Gomez, Perrone, Bobb, Lewis, McAtee
Sevilla lineup: Bono; Navas, Bade, Gudelj, Acuna; Jordan, Rakitic, Torres; Ocampos, El-Nesyri, Lamela
Subs: Dmitrovic, Gattoni, Pedrosa, Montiel, Suso, Mir, Tecatito, Sow, Gomez, Juanlu, Salas, Bueno