The exploding foil initiator (EFI) system has been extensively used in ignition and detonation sequences and proved to be of high safety and reliability. Polyimide is considered the ideal flyer material for EFI due to its excellent performance, including thermal stability, outstanding mechanical properties, high radiation resistance, and excellent dielectric properties. In this study, we prepared the EFI based on a polyimide (ODPA-ODA) flyer, which is spin-coated and solidified on patterned copper film in situ. The electric explosion test shows that the prepared EFI has good working performance, and the 4000 V working voltage drove the flyer to reach a maximum velocity of 5096 m/s. The polyimide morphology and chemical structure after the electric explosion was observed by microscope, SEM, XPS, and FTIR, which showed that the polyimide flyer underwent thermal deformation and complex chemical reactions during an electric explosion. A large number of polyimide bonds broke to form new carbonyl compounds, and the opening of aromatic rings was accompanied by the formation of aliphatic hydrocarbon chains. The morphology and chemical structure analysis after the electric explosion test will lay a foundation for us to further understand the working principle and evolution process of polyimide (ODPA-ODA) flyer.