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Pentafluorophenyl copper(I)–biarylsulfoxide complexes, existing as [Cu(C₆F₅)]₄L₂, both in solution and in the solid state, were prepared and thoroughly characterized. Subsequently, the photochemistry of the complexes was explored, showing inherent photoreactivity of the biarylsulfoxide moiety within the coordination sphere of the copper. Photoinduced cross-coupling reactions between the anthryl moiety of bis-anthracenylsulfoxide and pentafluorobenzene, and synthesis of Cu₂O (cuprite), were demonstrated.