8-(Phenylamino)-1-naphthalenesulfonates (1) exhibit variations in fluorescence maxima and quantum yields with solvent polarity and substituent change. These facts suggest sequential formation of two excited states, a naphthalene-excited S1,np state and a charge-transfer state, S1,ct’ as in the case of the 6-(phenylamino)-2-naphthalenesulfonates (2) (cf. Kosower, E. M. Acc. Chem. Res. 1982, 15, 259). An inefficient photochemical dissociation of the sulfonate group to form 1-(phenyl-amino)naphthalene is reported. Previously reported excited-state kinetics are consistent with the two-step mechanism.