AbstractThe paper reports the energization of Hydroxyl‐Terminated Polybutadiene (HTPB) by functionalizing explosophore NO2 over the HTPB backbone, resulting in the formation of conjugated nitro‐alkene derivative of HTPB. A convenient, inexpensive and efficient “one pot” procedure of synthesizing Nitro‐Functionalized Hydroxyl‐Terminated Polybutadiene (Nitro‐HTPB) is reported. The reaction was carried out with sodium nitrite and iodine. To retain the unique physico‐chemical properties of HTPB, functionalization by NO2 group was restricted to 10 to 15 % of double bonds. The Nitro‐HTPB was characterized by FTIR, 1H NMR, VPO, DSC, TGA etc. The polymer has shown good thermal stability for practical applications. The kinetic parameters for the decomposition of Nitro‐HTPB at 150–300 °C were obtained from non‐isothermal DSC data.