Poly(glycidyl azide) (PGA) an energetic polymer and polyepichlorohydrin (PECH) were condensed with 4,4’ azobis(4-cyanopentanoyl chloride) (ACPC) to prepare macro-azo-initiators. Block copolymers containing each of these polyethers as a block segment combined with polystyrene (PS) or poly(vinyl acetate) (PVAc) have been drived by the polymerization of monomers initiated with this macro-azo-initiators. Thermal properties of block copolymers were investigated with differential scanning calorimetry (DSC) and thermogravimetry. DSC traces showed single glass transition temperatures in between the related segments of copolymers. Dynamic thermogravimetric analysis revealed the individual degradation behaviors of block segments