In order to investigate influences of microstrucral Znic Oxide samples′ superficial nanotructure on their photoluminescence characteristics, ZnO sample with 2-Dimension network surface nanostructure was fabricated based on vapor phase transport method using zinc powder as a source. Their superficial structure was examined by X-ray diffraction pattern. Scanning electron microscopy picture and photoluminescence spectra excited with 355 nm laser pulse at room temperature were measured. The measuring results show that the structures are composed of three ordered multi-aperture gratings and the special photoluminescent properties, similar to structural colours, resulted from tne network surface, which works as photonic crystals here. The mechanism of this photoluminescent performance was discussed based on finite difference time-domain, rigious coupled-wave analysis methods and the reasonable explaination was present. Finally, the theoretically analysis conclusion was verified by experiment results.