Abstract: A process for the production of high molecular weight poly(vinyl ethers) and the like in which a selected monomer is polymerized in the presence of a metallocene-type catalyst is described. Vinyl ether monomers, N-vinylcarbazole and 1.5-10 hexadiene can be polymerized, in high yield using an initiator of the formula Cp*TiMe.sub.3 in the presence of a co-initiator of the formula B(C.sub.6 F.sub.5).sub.3. Novel dihydropyran polymers, such as poly 3,4-dihydropyran have also been produced.