Polystyrene with a benzyl ester of carboxylic acid at the center of a polymer skeleton was synthesized by living radical polymerization. The initiator used had two functional groups for 2,2,6,6-tetramethylpiperidinoxyl (TEMPO)-mediated living radical polymerization on the benzyl and the carboxylic sides of the benzyl ester. Introduction of the benzyl ester changed the polystyrene from a crosslink type to a scission type polymer on gamma-irradiation. Irradiation of the polymer resulted in a binary change of the molecular weight because of the dissociative capture of secondary electrons by the benzyl ester, as: MnR1COOCH(C6H5)R2Mn + e(-) --> MnR1COO- + (.) CH(C6H5)R2Mn The binary change of the molecular weight suggests that the polymer can be used as a new type of radiation resist with high sensitivity and spatial resolution to ionizing and high resistivity to plasma etching. The number of scissions per 100 eV radiation energy absorbed was 0.29, which was about one fourth of the yield of secondary electrons. The low efficiency was because of the recombination of polymer radicals generated by the dissociative electron attachment. (C) 2005 Wiley Periodicals, Inc.