The excitation mechanism of polycyclic aromatic amines (amino-PAHs) and polycyclic aromatic hydrocarbons(PAHs) for the chemiluminescence arising from the reaction between oxalate ester, bis(2,4,6-trichlorophenyl)oxalate (TCPO) or bis(2,4-dinitrophenyl)oxalate (DNPO) and hydrogen peroxide has been studied in terms of the excitation efficiencies to singlet excitation energies and the oxidative half-wave potentials. As a results of the study, the excitations of both amino-PAHs and PAHs appear to involve the charge transfer type of energy transfer. However the chemiluminescence efficiency corrected for fluorescence quantum yield of the amino-PAHs are varied more sensitively to the oxidative half-wave potential than that of PAHs possibly due to the large difference in solvation energy between the compounds and their ions.