1, 8-Naphthylimide (NI) was doped in polyvinyl alcohol (PVA) or polyacrylic acid (PAA) matrices (0.2%, mass ratio) to achieve persistent room-temperature phosphorescence (pRTP). The resulting pRTP can be attributed to the formation of a rigid environment constructed by abundant hydrogen bonds. Moreover, due to the overlap between NI's phosphorescent emission and Rhodamine B's absorption, the color-tunable persistent luminescence of RB@NI@PVA and RB@NI@PAA doped films were successfully achieved through phosphorescent resonance energy transfer strategy. This work provided an effective way to achieve the pRTP of NI by polymer doping, as well as persistent luminescence of Rhodamine B by phosphorescence resonance energy transfer from NI in the developed phosphorescent film system.