Photophysics of 1,8-naphthalimide (NAPMD) in different solvents has been delineated in this paper. Theoretically calculated bond distance of N–H and C=O groups rule out any intramolecular proton transfer in the excited state. Concomitant increase in negative charge on O atom compared to N atom and dipole moment hints at possible intramolecular charge transfer. Progressive redshift with polarity of solvents in emission and absorption spectra also confirms the theoretical prediction. Weakening of N–H bond helps hydrogen abstraction and anion formation in water with decay time of 2.54 ns through intermolecular proton transfer. This was corroborated from the ground state photoexcitation of laboratory synthesized anion of NAPMD. Amide hydrolysis in higher pH and excess proton availability at low pH are responsible for anion emission quenching. A possible electron transfer diminishes phosphorescence at 77 K with changing pH.