A new versatile method for conducting living radical polymerization has been developed in which organostibines induce consecutive group-transfer radical reactions with alkenes. The method has been successfully applied, for the first time, to the controlled polymerization of both conjugated and unconjugated vinyl monomers, and the desired polymers with predetermined molecular weight and low polydispersity index were obtained in excellent yields. This characteristic feature of this method is exemplified in the first synthesis of block copolymers composed of conjugated and unconjugated monomers, which would be of great importance as functional smart organic nanomaterials.