A study was carried out on radiation-induced cationic polymerization enhanced by the N-Alkoxypyridinium salt having relatively stable nonnucleophilic anion (PF,6,). After investigations on the cationic inhibitors, different atmosphere conditions and the molecular weight and its distribution, it was proved that the cationic polymerization to take place in CHO/ CH,2,Ｃl,2, or C,6,H,6,/ EMP,+,PF,6, system on irradiation with theγ-rays. The onium not only oxidated α-alkoxyalkyl radicals, produced from CHO in dichloromethane, to the correspondings cations, but also gave nonnucleophilic anions PF,6, for the polymerization system. A preliminary discussion is made on the effect of different polar solvents to reactive centers.