Abstract: SiO₂ microspheres were prepared by improving the Stöber method which added NaCl in solution systems for improving surface charge of the SiO₂ microspheres,and then SiO₂ photonic crystals were fabricated by the vertical deposition method at 40℃ and 60% relative humidity.The electrical properties,micromorphology and optical properties were characterized by Zeta potential instrument,Scanning electron microscope（SEM） with energy dispersive X-Ray spectroscopy and Uv-Vis-Nir spectrophotometer.Zeta potential of the modified SiO₂ microspheres in ethanol solution was averagely heightened 11.39mV;EDS spectra showed that there was Na element in microspheres;SEM images showed that the average size of modified SiO₂ microspheres was 334 nm,and its distribution standard deviation was less than 5%,and the sample of SiO₂ photonic crystals was face-centered cubic structure with its（111） planes parallel to the substrate;Absorption spectra showed that the existence of photonic band gap was at 725 nm.