Various aliphatic polyesters such as poly (ethyleneadipate), poly (tetramethylene adipate), poly (caprolactone), and poly (carbonate) were condensed with 4,4’-azobis-4-cyanopentanoyl chloride to prepare macro-azo-initiators. Their thermal properties, observed by differential scanning calorimetry, showed similar decomposition behavior to each other. Block copolymers containing each of these polyesters as a block segment combined polystyrene or poly (methylmethacrylate) have been derived by the polymerization of monomers initiated with these macro-azo-initiators.