Direct photoelectrochemical conversion of toluene (TL) to methylcyclohexane (MC) with water has been examined as an organic hydride conversion using light irradiation. The production of MC from TL was observed on Pt/CdS/Cu(2)ZnSnS(4)/Mo photoelectrodes with anion-type ionomer membrane assemblies. A cathodic photocurrent was observed below 0.7 V vs RHE (V(RHE)) in 0.1 M Na(2)SO(4)/NaOH (pH 9.5) aqueous solution, and an apparent photocurrent density of 0.5 mA cm(-2) was obtained at 0 V(RHE) under the irradiation of a 300 W Xe lamp with a 420 nm cutoff filter. The yield of MC was measured by gas chromatography, and an 88% faradaic efficiency was estimated. This study suggests the possibility of direct energy conversion from solar energy to MC as an energy carrier of organic hydrides.