We have verified the formation of exeiplex in the photopolymerization of AN ini-tiated with aromatic tertiary amines．From UV spectra and fluorescence spectra we are inclined to．believe that aromatic tertiary amine in the ground state will form charge-transfer complex (CTC) with AN which may be excited to exeiplex by irradiation (CTC excitation)，while in excited state it will also form exciplex with AN through local ex-citation．The order of photopolymerization rate of AN caused by loeal exciration is found to be CH3C6H4N(CH3)2>C6H5N(CH3)2>HOCH2C6H4N(CH3)2>CH3C6H4N(CH2CH2OH)2 and this is in agreement with the order of stern．Volmer constant for the quenching of fluorescence of amines by AN．The order of photopolymerization rate caused by CTC excitation is found to be CH3C6H4N(CH5)2>CH3C6H4N(CH2CH2OH)2>HOCH2C6H4N ·(CH3)2>C6H5N(CH3)2，which is in agreement with ability of donating electron of the substituted group on the benzene ring of aromatic amines．The presence of small amount of aromatic amine group a8 end-group in the polymer molecule has been deteeted by UV spectra．