In recent years, the development of perovskite solar cells (PSCs) is advancing rapidly with their recorded photoelectric conversion efficiency reaching 25.8%. However, for the commercialization of PSCs, it is also necessary to solve their stability issue. In order to improve the device performance, various additives and interface modification strategies have been proposed. While, in many cases, they can guarantee a significant increase in efficiency, but not ensure improved stability. Therefore, materials that improve the device efficiency and stability simultaneously are urgently needed. Some wide band‐gap insulating materials with stable physical and chemical properties are promising alternative materials. In this review, the application of wide band‐gap insulating materials in PSCs, including their preparation methods, working roles, and mechanisms are described, which will promote the commercial application of PSCs.