In this study, hierarchical ternary nanocomposites, i.e., Cu–TiO₂-mesoporous silica microspheres (Cu–TiO₂-MSM), were synthesized as ternary photocatalyst system to improve the visible light photocatalytic degradation of the environmental pollutant model dye methylene blue (MB). The innovation of this method is in situ depositing TiO₂ and Cu₂O nanoparticles sequentially onto the surface of mesoporous silica microspheres to form highly active heterostructure. The improved activity for the degradation of MB is attributed to: (1) the high adsorption capacity of the porous and interconnected-channel-structure MSM to MB; (2) the valence band electrons of TiO₂ released from the conduction band generating abundant highly active free radicals, which directly reacted with adsorbed MB. The photocatalytic degradation efficiency to MB was found to be 98% in 5 min, and almost 100% in 20 min. This study paves a way for the development of a ternary-doped catalyst for visible light photocatalytic degradation and may exhibit widely application in industry.