Metallic glasses (MGs), with their unique disordered atomic packing structure and superior catalytic capabilities, have gradually been realized with their significance in the field of catalysis. As a new type of promising catalyst, recent reports have demonstrated that MGs exhibit many excellent catalytic properties in wastewater treatment, such as ultrafast catalytic efficiency and reliable stability with a reduced metal leaching effect, etc. This review introduces, for the first time, recent developments in using MGs with various atomic components and excellent catalytic performance as environmental catalysts. In terms of the unique properties of MGs, this article provides a full discussion of several effects of their physical characteristics on catalytic reactivity, such as structural relaxation, crystallization, and rejuvenation, electronic structure, atomic configuration, thermophysical property, atomic composition, surface roughness, residual stress, and porosity by dealloying. The catalytic performance, including decolorization, mineralization, metal leaching, sustainability and reusability, as well as the effects of different chemical parameters, is systematically reviewed. This review also delivers several important prospects in further developing MG catalysts, offering new research opportunities into the study of their novel functional applications and providing new insights into the synthesis of novel catalysts.