ZnO nanoparticles were prepared by a simple chemical synthesis route. Subsequently, SiO2 layers were successfully coated onto the surface of ZnO nanoparticles to modify the photocatalytic activity in acidic or alkaline solutions. The obtained particles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS) and zeta potential. It was found that ultrafine core/shell structured ZnO/SiO2 nanoparticles were successfully obtained. The photocatalytic performance of ZnO/SiO2 core/shell structured nanoparticles in Rhodamine B aqueous solution at varied pH value were also investigated. Compared with uncoated ZnO nanoparticles, core/shell structured ZnO/SiO2 nanoparticles with thinner SiO2 shell possess improved stability and relatively better photocatalytic activity in acidic or alkaline solutions, which would broaden its potential application in pollutant treatment. Crown Copyright (C) 2010 Published by Elsevier B. V. All rights reserved.