A highly ordered ZnO/TiO2 photonic crystal (ZnO/TiO2-PC) was obtained by a simply pyrolysis strategy. Combined with a series of characterizations, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmittance spectra, it was found that the in situ formed ZnO phases were uniformly grafted to TiO2-PC framework forming hybrid nanostructure. Additionally, the formation of heterojunction between ZnO and TiO2-PC enhanced the separation efficiency of photogenerated electron-hole pairs, which significantly improved the photocatalytic performances. Based on the results of photoelectrochemical measurement and the detection of active species in photocatalytic degradation process, the photocatalytic degradation mechanism of ZnO/TiO2-PC nanocomposite was proposed. It is hoped that our work could provide a good insight into the preparation of photonic crystal heterostructures for the environmental purification. (C) 2015 Elsevier B.V. All rights reserved.