The first 4-enamine-N-methyl-1,8-naphthalimides (amine = piperidine, pyrrolidine, morpholine, Prn2NH, Pri2NH) are reported. The X-ray crystal structure of the piperidine derivative confirmed the E-stereochemistry and showed strong Π–Π stacking in the unit cell. The enamines are strongly fluorescent and quantum yields do not vary with the pKb of the amine. The solvent dependence of λ abs and λ flu is consistent with significant charge separation in the excited state.