[6][7] Having spent the first half of his debut season mostly on the sidelines, making only a few short appearances as a substitute, Thiaw emerged into the team's starting XI in February 2023 following his man of the match performance against Tottenham Hotspur in the round of 16 of the 2022–23 UEFA Champions League.

[8] As the team's head coach Stefano Pioli opted to change the formation from 4–2–3–1 to 3–5–2, Thiaw began to start every forthcoming game in the middle of the defensive third, with Fikayo Tomori on the left and Pierre Kalulu on the right.

[9] Ahead of the 2023–24 season, Thiaw and Tomori were the team's starting duo in central defense, with Kalulu and Simon Kjær as backups.

[10] The pair continued to play together until Thiaw's injury on 2 December 2023 in the game against Frosinone, which sidelined him for eight weeks.

[14] Aged just 21, he was called up to the Germany senior team by head coach Hansi Flick for the friendly matches against Peru and Belgium on 25 and 28 March 2023.