The poly(glycidylazide-co-terahydrofuran) [poly(GA-THF)] or GA-THF copolymers are recognized and established as high-energy binders in explosive systems. In present study, we have developed a greener approach for the syntheses of poly(glycidylazide-co-tetrahydrofuran) copolymers using microwave (MW) irradiation technique. Polymerization of epichlorohydrin and tetrahydrofuran was carried out in the presence of borontrifluoride etherate and ethylene glycol to afford polyepichlorohydrin-tetrahydrofuran (PECH-THF) copolymer followed by its reaction with sodium azide in DMF under microwave irradiation to give poly(GA-THF). The poly(GA-THF) copolymer and their precursors were characterized by various spectral techniques such as MS, H-1-NMR, C-13-NMR, UV-visible, and FTIR. The thermal analysis was done by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Molecular weights of these copolymers were determined using GPC techniques. Morphology of these copolymers was visualized using SEM. Our experimental study shows that the microwave irradiation was effective for the second step (azidation reaction) than conventional heating for the synthesis of GA-THF copolymers. Also, the benign syntheses were tackled and explored with range of solvents. Thus, the current methodology, might advent the researchers dealing with these high-energy binder materials in future.