Room-temperature phosphorescence materials have found important applications in dissolved oxygen sensing, temperature monitoring, anticounterfeiting, etc., because of their prolonged phosphorescence lifetime. However, the known systems mainly utilize the triplet local excited state emission, which is generally less sensitive to microenvironment perturbation. In this work, we designed a series of 4-phenyl-1,8-naphthalimide (NMI) derivatives containing different numbers of carbazole (Cz) units (denoted as NMI-Cz, NMI-2Cz, and NMI-3Cz). Steady state and time-resolved spectroscopy studies determined that the compounds undergo intramolecular through-space charge transfer in solution, yielding a triplet hybrid local charge transfer state. Room-temperature phosphorescence emission was observed in compound-doped poly(methyl methacrylate) thin films upon ammonia treatment. Interestingly, emission from different films exhibited different persistence times. We believe a film-based, time-resolved luminescent ammonia sensor could be developed by making a device of the emissive films as fabricated.