AbstractPhotochemical and photophysical processes leading to the formation of polymers with a conjugated double bond system under He‐Cd laser irradiation have been considered. Phenyl‐ and diphenylpropargylamines are utilized as monomers. The polymerization of these monomers is carried out only in the presence of an electron acceptor such as tetrabromomethane. The polymer formation process is directed to obtaining an intermediate compound followed by its polymerization. The polymerization of intermediate compound is carried out by cationic reaction of triple bond in the presence of electron acceptor. The polymer structure and properties have been investigated. The parameters of lightsensitive layers based on diphenylpropargylamine have been determi