Abstract: The end-groups of the polymers formed in photopolymerization initiated by aromatic amines,such as aniline,were identified with electron and fluorescence-spectro-photometric methods. The spectra show the presence of secondary and tertiary amino end-groups in the polymers formed with primary and secondary amine as initiators,respectively. These results suggest that the nitrogen radicals of the aromatic (primary and secondary amines,which were produced from the proton transfer in the exciplexes between amines and vinyl monomers,are also responsible for the initiation.