Although it is known that the efficacy of photoelectrocatalysts is enhanced by increasing the amount of high energy surface exposed, the development of a universal synthesis method with both superior activity and simplicity is needed for scalable applications. We herein controllably fabricated cuprous oxide (Cu2O) micro crystals with different morphologies, evolving from cubes, cuboctahedra, truncated octahedra and finally to octahedra on indium tin oxide (ITO) glass substrates, by a facile electrochemical deposition method. The structures of facet-engineered Cu2O samples and the underlying mechanism for the morphology evolution were investigated. The separation of photogenerated hole-electron pairs on Cu2O crystals with different exposed facets was characterized by measuring the photocurrent densities with chopped illumination, which increased with the increased concentrations of PVP: the octahedral Cu2O crystals, with the highest proportion of {111} facets exposed, exhibited the lowest electro-hole recombination in contrast to the cubes, cuboctahedra, and truncated octahedra, respectively. The photoelectrocatalytic degradation efficiency of the o-chlorophenol (2-CP) pollutant under sunlight irradiation with Cu2O-coated photocathode was further investigated to reveal the effect of different exposed facets. Due to the increased number of surface active sites available for degradation reactions, the octahedral Cu2O microcrystals presented higher photoelectrocatalytic activity compared to other shapes. Active oxygen species detected by electron spin-resonance (ESR) spectrometry implied that abundant superoxide radicals (O-2(center dot-)) were the dominant active radicals in the degradation. (C) 2017 Elsevier Ltd. All rights reserved.