Polycaprolactones due to the polar groups in their structures are able to be mixed with other nitrate esters and thus are presented as suitable binders. In the other hand, polyglycidyl nitrate with ONO2 groups is a high energetic polymer; however, it has not suitable mechanical properties. Consequently, it is possible to use the favorable mechanical properties of polycaprolactone and energetic properties of polyglycidyl nitrate by the synthesis of the PCL-PGN-PCL three-block copolymer. In this research, the PCL-PGN-PCL three-block copolymer was synthesized for the first time. Firstly, polyglycidyl nitrate as a monomer was synthesized using epichlorohydrin (60% total yield of the reaction). Then, polyglycidyl nitrate was synthesized by using this monomer (70% yield). Finally, the new PCL-PGN-PCL three-block copolymer was synthesized by ring opening polymerization of caprolactone as monomer and polyglycidyl nitrate (PGN) as a macro initiator in the presence of dibutyl tin laurate as catalyst. The differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were performed to investigate the thermal characteristics of this copolymer (Tg -45.2oC). In addition, there was one pick in the GPC chromatogram that proved the formation of PCL-PGN-PCL three-block copolymer. The PCL-PGN-PCL three-block copolymer was characterized by 1HNMR, 13CNMR and IR spectroscopy methods. In the last part, the synthesis process of the PCL-PGN-PCL three-block copolymer was optimized. The reaction conditions were optimized at 115oC for 19 hours using 1mol% of catalyst. Toluene was chosen as a solvent and the monomer was added gradually into the reaction media. The yield was 81%. Also, the molar ratio of monomer to initiator as 5: 1 showed the best molecular dispersity.