The polymerization of halogen-containing monomers, such as vinyl chloride, chloroprene [1–3], 2,3-dichloro-1,3-butadiene [4] and others in the presence of complex catalysts has a slow rate and large utilization of the catalyst (about 4% by weight of the monomer). Vinyl chloride [5] and compounds containing a reactive halogen atom, such as allyl chloride [6], allyl bromide [7], crotyl chloride [6], and other monomers of similar structure, are used to reduce the molecular weight (mol. wt.) of the polyolefins produced in the presence of titanium containing catalytic systems. For this reason, and also in order to clarify the causes of complex catalyst inactivation by the monomer with a reactive halogen atom, and the mechanism of their homopolymerization, we examined the polymerization of allyl chloride in the presence of vanadium-containing complex catalysts of cationic type. The study of the properties of pollyallyl chloride (PAC) (a close homologue of polyvinyl chloride), which is a model for the still unknown polypropylene chlorinated at the CH 3 group was also of special interest.