Multi-walled carbon nanotube (MWCNT)/zinc oxide (ZnO) hybrid were large scale synthesized by the reflux method in ethylene glycol with the aid of polyvinylpolypyrrolidone (PVP). The MWCNT/ZnO hybrid was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy spectra (EDS), X-ray photoelectron spectra (XPS), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), which have indicated uniform hybrid structure of 18 nm diameter ZnO coating on MWCNT surface. The photocatalytic performance of ZnO nanoparticles and the MWCNT/ZnO hybrid were investigated by removal of methylene blue. Consistent with the shift of its UV-vis diffuse reflectance spectroscopy (DRS) to shorter wavelengths, the heterostructure of MWCNT/ZnO hybrid induces an improvement in photocatalytic performance. The stability of the hybrid was characterized through cyclic photocatalytic test. Results indicated no observable performance degradation for MWCNT/ZnO photocatalyst even after ten recycles. (C) 2012 Elsevier B.V. All rights reserved.