Copolymerization of vinyl chloride (VC) and ethylene with Cp*Ti(OCH3)(3)/MAO catalyst was investigated. The Cp*Ti(OCH3)(3)/MAO catalyst initiated the copolymerization of VC with ethylene, although the copolymer yields were low. In the C-13 NMR spectra of the copolymers, the peaks based on junction part between VC and ethylene was observed, but the signals were small. From DSC measurement of the copolymers, only one glass transition temperature was observed. Thus, it is clear that the copolymerization with Cp*Ti(OCH3)(3)/MAO catalysts gave the copolymer, and the copolymer consisting of block sequence rather than random copolymer.