The living freeradicalpolymerizations of vinylacetate (VAc) were successfully achieved in the presence of a novel organic selenium compound (diselenocarbonates), with 2,2′‐azobisisobutyronitrile (AIBN) as the initiator. The living characteristics of the VAc polymerization were confirmed by the linear first‐order kinetic plots and linear increase of molecular weights (Mn) of the polymers with monomer