Pure light-atom organic phosphorescent molecules have been under scientific scrutiny because they are inexpensive, flexible, and environment friendly. The development of such materials, however, faces a bottleneck problem of intrinsically small spin-orbit couplings, which can be addressed by seeking a proper balance between intersystem crossing (ISC) and fluorescence rates. Using N-substituted naphthalimides as the prototype molecule, we applied chemical modifications with several electrophilic and nucleophilic functional groups, to approach the goal. The selected electron donating groups actively restrain the fluorescence, enabling an efficient ISC to the triplet manifold. Electron withdrawing groups do not change the luminescent properties of the parent species. The changes in ISC and fluorescence rates are related to the nature of the lowest singlet state, which changes from localized excitation into charge-transfer excitation upon configuration change of excited molecules. This finding opens an alternative strategy for designing pure light-atom organic phosphorescent molecules for emerging luminescent materials applications.