The polymerization of vinyl chloride (VC) with vanadium complex/alkylaluminum catalyst was investigated. In the case of polymerization with vanadium oxytriethoxide (VO(OEt)(3)), poly(vinyl chloride) was obtained in a good yield. The effect of cocatalyst, solvent, and cocatalyst/precatalyst ratio was observed. The structure of the polymer obtained with VO(OEt)(3)/i-Bu3Al catalyst consisted of regular head-to-tail sequence and isobutyl chain-end structure. VO(OEt)(3)/alkylaluminum catalyst was able to copolymerize VC with styrene, 1-butene, methyl methacrylate, and methyl acrylate. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1006-1012, 2011