A novel oxidation state modulation mechanism, merging oxidative quenching (IrIII-*IrIII-IrIV-IrIII) and nickel catalytic (NiII-NiI-NiIII-NiI-NiII) cycles, has been illuminated unambiguously for photoredox-mediated iridium(iii)/nickel(ii) dual catalyzed C-O cross-coupling of aryl bromide and alcohol. Quinuclidine participates in a crucial proton-coupled electron transfer process to accelerate the reaction and regulate C-O coupling selectivity.