Novel dibenzylpiperidinium salts with non-nucleophilic anions (DBPi-SbF6, DBPi-PF6) have been prepared as latent cationic initiators. Utility of these salts in the photo and thermal-induced cationic polymerizations of epoxide and vinyl ether monomer systems has been studied. The new initiator, DBPi-SbF6 showed good solubility, high reactivity, and high thermal latency for polymerizations of epoxide and vinyl ether monomers with only 1 wt % of concentration. Cationic polymerization of vinyl ether monomer was significantly faster than epoxide monomer by the synthesized initiators. This article describes the synthesis, characterization, and activity of novel initiators. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 1878-1883, 2009