CaWO4:Eu3+/SBA-16 composites with various molar ratios of Eu3+ to CaWO4(x) were successfully synthesized by impregnation and subsequent hydrothermal treatment. The physicochemical properties of the resultant composites were well characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N2 adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR) and luminescence spectra. The results demonstrated that the resultant CaWO4:Eu3+/SBA-16 composites still had ordered mesostructure, i.e., the loading of CaWO4:Eu3+ has little impact on the uniform mesostructure of the host matrix SBA-16, but just reduced the specific surface area and pore volume of the host matrix. Furthermore, the CaWO4:Eu3+/SBA-16 composites with various x showed enhanced luminescent properties than the pure CaWO4:Eu3+ counterparts, and reached the highest luminescence intensity when x was 3%.