In this study, optical stop band of three-dimensional silica shell photonic crystals is tuned by adjusting inner diameter and shell thickness of hollow silica spheres. The silica shell photonic crystals are fabricated by sintering crystalline arrays, which are assembled from polystyrene/silica core–shell spheres by an improved vertical deposition method. The inner diameter and the shell thickness are controlled by diameter of polystyrene spheres and concentration of tetraethoxysilane. The results of transmission spectra show that there is an evident red shift of optical stop band as the inner diameter and the shell thickness increase. The red shift of optical stop band is due to variations in the inter-planar spacing and the effective refractive index of silica shell photonic crystals, which result from the variations of the inner diameter and the shell thickness of hollow silica spheres.