In this paper, using hollow silica microspheres as carriers, we developed a facile one-pot method for the preparation of hollow SiO₂@MnO₂ composite microparticles. Under a certain proportion of hollow silica microspheres and manganese salt, a novel kind of hollow urchin-like SiO₂@γ-MnO₂ microparticles was obtained. The structure and morphology of the composite microparticles were characterized by XRD, SEM and TEM. On this basis, using rhodamine B and methyl orange as model molecules, the oxidative degradation ability of the hollow SiO₂@γ-MnO₂ microparticles for organic dyes in water was investigated through UV-vis analysis technology. The urchin-like SiO₂@γ-MnO₂ microparticles showed excellent performance for the rapid oxidative degradation of organic dyes under acidic conditions. This study indicated that γ-MnO₂ loaded on hollow materials can be used as an efficient tool for treating organic dye wastewater, and shows broad application prospects for solving environmental problems in the related industry.