A　new　cross-coupling　of　trifluoromethyl　arenes　has　been　realized　via　multiphoton　photoredox　catalysis.　Trifluoromethyl　arenes　were　demonstrated　to　undergo　selective　mono-defluorinative　alkylation　under　mild　reaction　conditions　providing　access　to　a　series　of　valuable　α,α-difluorobenzylic　compounds.　The　reaction　shows　broad　substrate　scope　and　general　functional　group　tolerance.　In　addition　to　the　electron-deficient　trifluoromethyl　arenes　that　are　easily　reduced　to　the　corresponding　radical　anion,　more　challenging　electron-rich　substrates　were　also　successfully　applied.　Steady-State　Stern-Volmer　quenching　studies　indicated　that　the　trifluoromethyl　arenes　were　reduced　by　the　multiphoton　excited　Ir-based　photocatalyst.　©　2024　Wiley-VCH　GmbH.