The development of mild and efficient process for the selective oxidation of organic compounds with molecular oxygen can be one of the key technologies for synthesizing oxygenates. Here, a visible light-driven metal chloride to catalyze the selective oxidation of cyclohexane was carried out at ambient temperature under a pure O-2 atmosphere. Among the metal salts examined, only a few metal chlorides, with easily changeable valence, such as CuCl2 center dot 2H(2)O, VOCl3, and FeCl3 center dot 6H(2)O, were found to be active to this photo-oxidation reaction in acetonitrile or acetone, providing cyclohexanol, cyclohexanone, chlorocyclohexane, and cyclohexene as main products. This is likely because the weak coordination of these metal chlorides with solvent molecules plays key roles in absorbing visible light and realizing photoredox cycle, as supported by UV-Vis spectrum and cyclic voltammetry measurements. Among these active metal chlorides, CuCl2 center dot 2H(2)O showed a higher conversion and better selectivity for cyclohexanol and cyclohexanone (the oxygenated products) than the other two metal chlorides, and its activity and selectivity for chlorocyclohexane were significantly improved in the case of adding concentrated HCl, because HCl promotes the photocatalytic cycling, as supported by UV-Vis spectra. Notably, a high turnover frequency (TOF, 7.4 h(-1)) and an excellent selectivity for the oxygenated products (93%) were achieved upon a low concentration of CuCl2 center dot 2H(2)O (0.002 mol L-1), 0.1 ml of concentrated HCl and 2 atm of O-2 pressure. Based on these findings, a free radical mechanism for the present photocatalysis system was proposed. (C) 2011 Elsevier Inc. All rights reserved.