Polystyrene latex (PS) spheres and EO20PO70O20 (P123) were used as dual template agents, with TiO2 as the matrix, to prepare a three-dimensionally ordered macroporous (3DOM) composite Bi2O3/TiO2, using a sol-gel method and post-processing calcination. The phase structures, chemical composition, morphology, and surface physicochemical properties were characterized using X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), ultraviolet-visible diffuse reflectance (UV-Vis DRS) and X-ray photoelectron spectroscopies (XPS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electron microscopy (SEM), and N2 adsorption-desorption measurements. The results show that the composite is well crystallized and has a highly ordered porous structure with mesoporous walls; it is a 3DOM material. The light absorption of 3DOM-Bi2O3/TiO2 is red-shifted by about 60 nm to the visible region compared with TiO2. In the photocatalytic