B2O3-P2O5-SiO2 (BPS) three-dimensional (3D) high-organized polystyrene (PS) opals and inverse opals with large domain were fabricated and characterized. Scanning electron microscope (SEM) shows three or four small "windows", indicating that a very well interconnection between PS spheres of opal. The ultraviolet-visible (UV-vis) spectra indicate that the photonic band gaps (PBGs) are about 710 and 604 nm for 320- and 270-nm spheres respectively. While according to Bragg's equation, the simulation results should be 762 and 643 nm, which mean that 52 and 39 nm were shifted to blue region, respectively.