A new energetic thermoplastic elastomer based on the azidated polybutadiene(Az-PBD)/ethylene vinyl acetate copolymer (EVA) blends was prepared, and structure and properties of the blends were invetigated by SEM, DSC, DMA, tensile testing and combustion test. The Az-PBD was synthesized via a two-step process involving the addition reaction of commercially available 1,2-PBD with Br2 and subsequent nucleophilic substitution reaction of the brominated PBD with NaN3. EVA/Az-PBD with 90/10, 80/20, 70/30 (wt/wt) was prepared by a solution blending. SEM, DSC, and DMA results revealed that the blends are partially compatible and Az-PBD is dispersed in continuous EVA matrix. Tensile test showed that modulus and tension set increased while elongation-at-break of the blends decreased with increasing Az-PBD content in the blends, but all the blends showed a elongation at break as high as 700% and a tension set of less than 5%, indicating that the blends are typically elastomeric. Combustion test showed that, with increasing Az-PBD content in the blend, higher energy can be released.