Graphene-based materials have aroused enormous focus on a wide range of engineering fields because of their unique structure. One of the most promising applications is gas adsorption and sensing. In electrical engineering, graphene-based sensors are also employed as detecting devices to estimate the operation status of gas insulated switchgear (GIS). This paper reviews the main synthesis methods of graphene, gas adsorption, and sensing mechanism of its based sensors, as well as their applications in detecting SF6 decomposing products, such as SO2, H2S, SO2F2, and SOF2, in GIS. Both theoretical and experimental researches on gas response of graphene-based sensors to these typical gases are summarized. Finally, the future research trend about graphene synthesis technique and relevant perspective are also given.