A film of copper complex [CuL](NO3)(2) (L = 2,3,8,9-tetraphenyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene) formed on indium tin oxide (ITO) coated glass by the solvent evaporation of the acetonitrile solution of the complex onto the ITO substrate, was characterized by ultraviolet-visible absorption spectroscopy, cyclic voltammetry, scanning electron microscopy, and photoelectrochemistry. The photoelectrochemical cell by using [CuL](NO3)(2) modified ITO, a saturated calomel electrode, and platinum wire as working, reference and counter electrodes respectively in 1 M Na2SO4, was found to exhibit a large prompt and reproducible cathodic photocurrent density of 71 mu A/cm(2) under white light irradiation of 70 mW/cm(2) at an applied potential of -0.4 V, and an incident photon to current efficiency (IPCE) of 1.1% at lambda = 660 nm. This Cu(II) complex photosensitizer has advantages of simple synthesis, low-cost, environmentally benign and good photoelectrochemical performance. (C) 2011 Elsevier Ltd. All rights reserved.