New polyfunctional vinyl ether monomers are synthesized by the regioselective addition reactions of glycidyl vinyl ether (1) with acyl chlorides, silyl chlorides, and phosphonic chlorides catalyzed by quaternary onium salts. Polyfunctional vinyl ether monomers containing silicone or phosphorus are also synthesized by the regioselective reaction of 1 with silyl chlorides or phosphonic chlorides. Vinyl ether oligomers are synthesized by the polycondensation of the vinyl ether monomers, which have reactive chloromethyl groups, with dicarboxylic acids. Hybrid type vinyl monomers and oligomers are successfully synthesized by the reaction of the synthesized vinyl ether monomers with unsaturated carboxylic or dicarboxylic acids using DBU as a base. Reaction behaviors of photoinitiated polymerizations of the new vinyl ether monomers, hybrid-type vinyl monomers, and oligomers in bulk under UV irradiation were investigated in detail.