After years of trying to secure the services of Mbappe, the Spanish giants got their man when he signed a five-year deal at the Santiago Bernabeu in June as a free agent after ending his association with Paris Saint-Germain.
The France captain will now be thrown in at the deep end in his new club's first official game of the campaign, which offers him the chance to win his first European trophy.
Mbappe helped France reach the semi-finals of Euro 2024 although he endured a difficult tournament in Germany, breaking his nose in his country's opening game and only scoring one goal, from a penalty.
The 25-year-old was then unveiled before 80,000 fans at the Bernabeu before being afforded a holiday, meaning he played no part in Real's pre-season tour of the United States.
Therefore, Mbappe's debut in the Polish capital will come just a week after he completed his first training session with Carlo Ancelotti's squad.
"Kylian can play from the start just like everyone who is here," Ancelotti said in Warsaw on the eve of the game.
"He is adapting really well, he is focused and he is showing extraordinary quality."
Media back in Spain are licking their lips at the prospect of seeing Mbappe in action for Real at long last.
'Superdebut'
The two major sports dailies in the Spanish capital splashed the same picture of the striker in training on their front pages on Wednesday.
"Superdebut" was the headline on the cover of AS, while rival publication Marca went with KM0, using the new signing's initials to signify "Kilometre Zero" ahead of his first game.
Ancelotti, meanwhile, laughed off suggestions that fitting Mbappe into a side that won the Champions League last season could somehow be a problem.
"I have been thinking about this all summer. Who to play and who not to play. It has ruined my holidays," joked the Italian.
Real already had Vinicius Junior, Jude Bellingham and Rodrygo in attack, while Mbappe is not the only new recruit, with Brazilian prodigy Endrick also having arrived from Palmeiras.
Toni Kroos and Nacho have departed since Madrid were crowned European champions for the 15th time at the start of June, while Eduardo Camavinga is out of Wednesday's game after injuring a knee in training.
Atalanta are contesting the Super Cup for the first time after winning last season's Europa League, their first piece of European silverware.
The Italian club are without striker Gianluca Scamacca, who tore the anterior cruciate ligament in his left knee at the start of the month.
However, they have signed another Italian international striker in Mateo Retegui, who has joined from Genoa.
Last season's Super Cup was won by Manchester City, who beat Sevilla on penalties.
Recent UEFA Super Cup winners
2023: Manchester City (ENG)
2022: Real Madrid (ESP)
2021: Chelsea (ENG)
2020: Bayern Munich (GER)
2019: Liverpool (ENG)
2018: Atletico Madrid (ESP)
2017: Real Madrid (ESP)
2016: Real Madrid (ESP)
2015: Barcelona (ESP)
2014: Real Madrid (ESP)