Arc explosion accidents in live working seriously threaten the safety of power workers. At present, the mainstream arc protective clothing material is aramid and blends of aramid. However, aramid will produce toxic gas under high temperature combustion, which is harmful to the health of operators. Therefore, it is a special challenge to study fabrics that are friendly to the human body and have a highly protective performance to protect electrical workers. Polyimide is nontoxic and has excellent high temperature resistance, flame retardation, and mechanical properties. In this paper, polyimide was proposed to be used as an arc protective clothing material. In order to explore the feasibility of polyimide in the field of arc protection, molecular dynamics simulation was used to compare the heat resistance of polyimide and aramid in terms of bond order and glass transition temperature. Referring to ASTM F1959 and IEC 61482-1-1, an arc test apparatus was built to test the protective properties of materials. The protection failure mechanism was analyzed by comparing the safety protective performance of polyimide and aramid fabric under the arc. It was found that polyimide has better arc thermal protective performance and break open threshold. The simulation and test results show that polyimide can be used as a material for arc protective clothing to improve protective performance.