To improve the reinforcement effect between a binder and high solid filler in a propellant formula, grafting the bonding group into the binder to form a neutral polymeric is a practically novel approach to improving the interface properties of the propellant. In this work, a glycidyl azide polyol energetic thermoplastic elastomer binder with a –CN bonding group (GAP–ETPE) was synthesized, and the mechanical and thermal decomposition mechanism of GAP–ETPE with Hexogeon (RDX) model propellants were studied. The stress–strain results indicated that the tensile strength and strain of GAP–ETPE/RDX model propellants were 6.43 MPa and 32.1%, respectively. DMA data showed that the storage modulus (E’) of the GAP–ETPE/RDX model propellants could increase the glass transition temperature (Tg) values, those were shifted to higher temperature with the increase in filler RDX percentages. TG/DTG showed the four decomposition stages of the decomposition process of the GAP–ETPE/RDX model propellants, and the thermal decomposition equation was constructed. These efforts provide a novel method to improve GAP–ETPE/RDX propellants mechanical property, and the thermal decomposition behavior of GAP–ETPE/RDX propellants also provided technical support for the study of propellant combustion characteristics.