In this study, polystyrene- and poly(methyl methacrylate)-grafted polyimide films were prepared successfully using click chemistry and the ATRP technique. Firstly, kapton films were prepared from stepwise thermal imidization of polyamic acid. Surface modification of kapton films was then achieved by chloromethylation followed by the azide decoration process. For surface grafting of kapton films, polystyrene and poly(methyl methacrylate) as alkyne functional polymers were prepared with alkyne and bromine double functionality using propargyl-2-bromopropionate as an initiator. A coupling reaction with azide-decorated PI surface and alkyne functional polymers was achieved via the Huisgen-1,3-dipolar cycloaddition reaction. FTIR spectroscopy, contact angle measurement, thermogravimetry (TG) and differential scanning calorimetry (DSC), energy dispersive X-ray analysis (EDX) and GPC techniques were used to characterize the grafted polyimides. According to the TG analysis, kapton film was modified at the rate of 8% and 10% with PS and PMMA, respectively.