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The radical telomerization of vinyl chloride with carbon tetrabromide was investigated. The telomers with n=1 and 2 in Br(CHClCH2)nCBr3 were isolated and identified. The molecular weight distribution of the telomers was determined by thin-layer chromatography (TLC), and it was found that the distribution varied a little with the variation of reaction conditions. From the results of the TLC, the chain transfer constants (Cn) of polylvinyl chloride radical to carbon tetrabromide were calculated, and a monotonous increase in Cn with the increasing n was found. The effects of initial ratio of vinyl chloride to carbon tetrabromide, reaction time and temperature on the conversion of vinyl chloride and the average molecular weight of the telomer were investigated. Bromoform was also used as a telogen instead of carbon tetrabromide, and the results were compared in both systems.