Inverse opal (IO) macroporous semiconductor materials with unique physicochemical advantages have been widely used in solar-related environmental areas. In this minireview, we first summarize the synthetic methods of IO materials, emphasizing the two-step and three-step approaches, with the typical physicochemical properties being compared where applicable. We subsequently discuss the application of IO semiconductors (e.g., TiO2, ZnO, g-C3N4) in various photo-related environmental techniques, including photo- and photoelectro-catalytic organic pollutant degradation in water, optical sensors for environmental monitoring, and water disinfection. The engineering strategies of these hierarchical structures for optimizing the activities for different catalytic reactions are discussed, ranging from heterojunction construction, cocatalyst loading, and heteroatom doping, to surface defect construction. Structure-activity relationships are established correspondingly. With a systematic understanding of the unique properties and catalytic activities, this review is expected to orient the design and structure optimization of IO semiconductor materials for photo-related performance improvement in various environmental techniques. Finally, the challenges of emerging IO structured semiconductors and future development directions are proposed.