A series of polyimide films irradiated by 170 keV N+and 120 keV B+with controlled and related implantation conditions were investigated with respect to their microstructures in modified layers, as well as their application prospects as temperature sensors. The sensitivities and sensitive ranges of these functional materials were correlated with the implantation conditions in terms of the Raman spectroscopic results. This well‐defined relationship was interpreted with perspectives of ion beam microstructural modification, which provides a deeper insight into the fundamental aspects for the synthesis of temperature‐sensitive materials out of polyimide precursor. It seems that greater irradiation dose, stronger beam current density, and higher target temperature constitute a set of favorable conditions for the fabrication of temperature sensors with a comparatively broad sensitive scope.