Model compounds and polymers having N-substituted 1,2-diphenylmaleimide moieties were synthesized and characterized by NMR, IR, UV, and fluorescence spectroscopy. The fluorescence intensity could be controlled by N-substituents of model compounds and polymers. As the structure of an N-substituent of them was bulkier, or the electron density of an N-substituent was denser, the photoluminescence intensity was increased. All the compounds showed greenish yellow photoluminescence with the maximum intensity between 510 and 537 nm. From quantum efficiency data of the model compounds and the polymers, the fluorescence intensity of the polymer 11 was higher than that of the model compound 4.