It displays a favorable spherical morphology of the energetic RDX@NGEC nanocomposites and the 3D distribution of Raman mapping images, as well as the gas products detected by IR, and the mechanism of the desensitization. • Electrospray technology is utilized to assemble a novel energetic RDX@NGEC nanocomposites successfully. • The obtained RDX@NGEC composites exhibit favorable thermal decomposition and significant reduced sensitivity. • The mechanism of coating process, thermal decomposition and desensitization was proposed and discussed. • This construction strategy of novel energetic binder NGEC-based composites provides an application potential in propellants. Recently, an emerging category of thermal plastic energetic binder: nitrate glycerol ether cellulose (NGEC) exhibits promising application in propellants with extraordinary mechanical performance, and can be considered for using in military system instead (or partial) of traditional nitrocellulose (NC). In this paper, the electrostatic spraying technology is performed to synthesis a novel kind of nanocomposites energetic materials (nEMs) (hexahydro-1,3,5-trinitro-1,3,5-triazine) RDX@NGEC by adjusting the mass ratio of NGEC:RDX (0:5 ∼ 2.5:2.5). The results demonstrate that the NGEC patches with content of 30% were coated relatively uniformly on the surface of RDX crystal, and an ideal spherical structure, with dramatically reduced particle size (100 ∼ 800 nm) was obtained. Most importantly, the thermal decomposition properties are investigated systematically by traditional DSC (differential scanning calorimeter) analysis, DSC-TG-IR (DSC-thermogravimetric analysis-fourier-transform infrared spectroscopy) combining technology, where the kinetic parameters of thermal decomposition reaction are also calculated by two traditional methods: the Kissinger and Ozawa methods. It reveals that the process of the decomposition is mainly controlled by RDX when content of NGEC is low (10%∼20%), and the decomposition peak of NGEC is gradually appearing with the increasing content of NGEC (30%∼50%). Furthermore, the impact and friction sensitivities are tested and have been reduced about 1 ∼ 3 times. The mechanism of the sensitivity reduction, coating process and decomposition are also discussed detailly. Hence, this preparation and properties strategy of novel energetic RDX@NGEC nanocomposites may provide foundational theory research and exhibits application potential in propellants and explosives.