The proficiency of the cyclometalated iridium complexes [(η⁵-C₅Me₅)IrCl(L1)] (1), [(η⁵-C₅Me₅)IrCl(L2)] (2) and [(η⁵-C₅Me₅)IrCl(L3)] (3) has been examined towards photochemical water oxidation. The involvement of Ir(IV/V) in the catalytic process has been explored via CV, UV/vis, XPS spectroscopic studies and appreciable TON relative to the theoretical value of 1 from GC.