A fluorescence imaging system is designed based on the photodecomposition of photobase generators embedded in polyvinyl butyral (PVB) matrix. These photobase generators were synthesized with propyl and phenethyl units served as leaving groups, and phthalimido, succinimido, di-2-thienyl ketoximino, and benzophenoneoximino units acted as photosensitive species, respectively. The influences of the two leaving groups and four photosensitive species on the photochemical behavior were investigated in detail. The results demonstrate that the photochemical properties of these photobase generators depend on the photosensitive species other than the leaving groups. And further study shows that succinimido propylcarbamate (SPrC) exhibits the best thermal stability and relatively quick rate of photodecomposition among all the photobase generators. Therefore, a PVB film embedded with SPrC is used as a fluorescence imaging material. The patterned fluorescence image obtained from the fluorescamine-treated irradiated PVB film showed bright green fluorescence, which provides potential application for optical storage or color electronic displays. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41058.