We report the synthesis of copper-doped zinc oxide microstructures with a large amount of polar surfaces using a single-step facile chemical method by collecting powders of zinc oxide (ZnO) microstructures. It was found that rod-like morphology of ZnO transformed into disk and sphere-like structure with nanosheets. Hollow disk-like structures were formed due to the surface etching properties of Cl- ions in the copper chloride precursor. The photocatalytic degradation of methylene blue (MB) and rhodamine B (RhB) dyes was measured under irradiation with visible light using the structures as catalysts. The Cu-doped ZnO exhibited better photodegradation properties than did undoped ZnO. The enhanced performance is attributed to the existence of (001) polar surfaces, oxygen vacancies, and increased optical absorbance at visible wavelengths, which is consistent with the field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), room temperature photoluminescence (PL), and optical absorbance measurements. These favorable photocatalytic properties of the doped microstructures demonstrate their potential for use in wastewater treatment. (C) 2014 Elsevier B.V. All rights reserved.