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The centre-back went through Borussia Dortmund's youth academy. In 2017, Luca Kilian won the under-19 German championship with BVB. After his first season in men's football with Dotrtmund's under-23s in the Regionalliga West, Kilian moved to Bundesliga side SC Paderborn 07 in summer 2019. There, the former Germany under-21 international made his debut under Steffen Baumgart in the 2019-20 campaign.
In the 2020-21 season, Kilian moved to 1. FSV Mainz 05. A year later, he was loaned out to 1. FC Köln before being signed on a permanent basis. The centre-back is often described as being the funniest team-mate. His childhood hero is Mats Hummels.