A novel allyloxy-picolinium salt, N-[2-(methyl)allyloxy]-alpha-picolinium hexafluoroantimonate, has been synthesized and used as addition-fragmentation agent for radical promoted thermal and photochemical cationic polymerization of monomers such as cyclohexene oxide, p-methoxystyrene and various vinyl ethers. Polymerization by heat was achieved using the allylic salt in conjunction with benzoyl peroxide (BPO), phenylazotriphenylmethane (PAT) and 2-2'-azobis-isobutyronitrile (AIBN). Polymerization rates were found to drop in the order PAT > BPO > AIBN. Photopolymerization was carried out by irradiating the allyloxy-picolinium salt in the presence of monomer at 280nm. Upon adding benzoin as free radical source, the spectral response was extended to 370 nm. The initiation mechanism is explained in terms of an addition-fragmentation scheme.