In this study, an original radiolytic method, based on pulsed electron beam irradiation, is used for the synthesis of conducting PEDOT in an aqueous solution containing EDOT monomers in the presence of potassium persulfate, K 2 S 2 O 8 , at 0 °C. At this low temperature, EDOT monomers are not chemically oxidized by S 2 O 8 2− anions, initiating PEDOT polymerization, but are rather oxidized by sulfate radicals, SO 4 •− , which are radiolytically generated by the reaction of solvated electrons, produced by water radiolysis, with persulfate anions. Successfully, as demonstrated by UV–vis absorption spectrophotometry and ATR-FTIR spectroscopy, irradiating the aqueous solution, by using a series of accumulated electron pulses, enables complete EDOT oxidation and quantitative in situ PEDOT polymerization through a step-by-step oxidation mechanism. The morphology of PEDOT polymers, mixed with unreacted K 2 S 2 O 8 salt, is characterized by Cryo-TEM microscopy in aqueous solution and by SEM after deposition. Successfully, in the absence of any washing step, high resolution AFM microscopy, coupled with infrared nanospectroscopy, is used to discriminate between the organic polymers and the inorganic salt and to probe the local chemical composition of PEDOT nanostructures. The results demonstrate that PEDOT polymers form globular self-assembled nanostructures which preferentially adsorb onto unreacted K 2 S 2 O 8 solid nanoplates. The present results first demonstrate the efficiency of sulfate radicals as oxidizing species for the preparation of nanostructured PEDOT polymers and second highlight the promising potentiality of electron accelerators in the field of conducting polymers synthesis. [ABSTRACT FROM AUTHOR]