AbstractPolyimide (PI) films equipped on the surface of spacecraft are susceptible to ultraviolet damage. Herein, the performance of two kinds of polyimide films i.e. 3,3′,4,4′-biphenyl dianhydride-p-phenylenediamine (BPDA-PDA) and pyromellitic dianhydride-4,4′-oxydianiline (PMDA-ODA) under vacuum ultraviolet (VUV, 172 nm) irradiation was studied. The failure behavior of the PI films was studied by tensile tests, thermogravimetry (TGA), thermomechanical analysis (TMA), electric breakdown, UV–visible transmittance and scanning electron microscopy (SEM). Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to analyze the molecular structure. The results indicated that the tensile strength of BPDA-PDA PI and PMDA-ODA PI films decreased by 10.4 and 7.4% under VUV irradiation, respectively; the breakdown strength and UV-transmittance also deteriorated. Besides, the surface morphology of the PI films showed a large number of microcracks after VUV irradiation, which we ascribe to the breakage of imide rings (C-N-C) and ether bonds (C-O-C) of the PI films. However, the thermal stability (residual weight) of both PI films remained constant compared to the initial level; this can be explained by the combined effect of bond breaking and cross-linking of the polyimide films.Keywords: Polyimide filmvacuum ultravioletproperty evolutionmolecular structure AcknowledgementsJiaqi Chen and Tingting Zhao contributed equally to this work.Disclosure StatementThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.Additional informationFundingThis work was supported by National Key Research and Development Program of China (No. 2020YFA0711700) and Industrialization Project of Xiangyang Technology Transfer Center of Wuhan University of Technology (WXCJ-20220010).