In recent decades, with the rapid development of the inorganic synthesis and the increasing discharge of pollutants in the process of industrialization, hollow-structured metal oxides (HSMOs) have taken on a striking role in the field of environmental catalysis. This is all due to their unique structural characteristics compared to solid nanoparticles, such as high loading capacity, superior pore permeability, high specific surface area, abundant inner void space, and low density. Although the HSMOs with different morphologies have been reviewed and prospected in the aspect of synthesis strategies and potential applications, there has been no systematic review focusing on the structures and compositions design of HSMOs in the field of environmental catalysis so far. Therefore, this review will mainly focus on the component dependence and controllable structure of HSMOs in the catalytic elimination of different environmental pollutants, including the automobile and stationary source emissions, volatile organic compounds, greenhouse gases, ozone-depleting substances, and other potential pollutants. Moreover, we comprehensively reviewed the applications of the catalysts with hollow structure that are mainly composed of metal oxides such as CeO₂, MnO_x, CuO_x, Co₃O₄, ZrO₂, ZnO, Al₃O₄, In₂O₃, NiO, and Fe₃O₄ in automobile and stationary source emission control, volatile organic compounds emission control, and the conversion of greenhouse gases and ozone-depleting substances. The structure–activity relationship is also briefly discussed. Finally, further challenges and development trends of HSMO catalysts in environmental catalysis are also prospected.