The side polyimide containing azobenzene group was synthesized with photochromism property from 2,2-Bis (3-amino-4-hydroxyyphenyl) hexafluoropropane (6FHP), pyromellitic dianhydride (PMDA) and dispersed red 1 (DR1). The chemical structure and thermal properties of polyimide were characterized using Fourier transform infrared (FT-IR), ultraviolet-visible (UV-Vis) spectroscopy, differential scanning calorimeter (DSC), and thermal gravimetric analysis (TGA). The DSC and TGA exhibited the glass transition temperature (Tg) and the decomposition temperature (Td) of polymer were 298 ℃ and 365 ℃, respectively. These results showed that the material had excellent thermal stability. The UV-induced trans/ cis photoisomerization and the thermal reflex-isomerization behavior were investigated for the polymer in solution and in film. The results indicate that the polymer solution and polymer film can undergo photochromism after a given UV wavelength (365 nm) photoinduction. This showed that the polyimide could be used to carry out perpetuity photoinduced birefringence and recording.