We have fabricated three-dimensional ZnO photonic crystals by the self-assembly of SiO2/ZnO core–shell microspheres of diameter 180–220 nm by means of a vertical deposition method. The organized crystals adopt a uniform close-packed hexagonal structure with long-range order and a high filling fraction. They exhibit strong partial photonic band gaps at 565–688 nm in the transmission spectrum and a broadened band edge emission at 383 nm in the photoluminescence spectrum. For comparison with these ZnO photonic crystals, we have also prepared pure silica crystals of the same dimensions. The photonic band gaps of the former have been found to be shifted to a longer wavelength by about 200 nm compared to those of the latter as a result of the higher refractive index of ZnO. This approach provides an efficient, economical alternative means of obtaining other, more complicated photonic crystals.