Development of ultra-fine fiber technology and nano-sized materials are widely taking place to enhance the characteristic of different materials. In our study, a newly developed technique was used to produce improvised nano energetic fibers with the exploitation of cis‐1,3,4,6‐Tetranitrooctahydroimidazo‐[4,5‐d] imidazole (BCHMX) to spin in a polystyrene nanofiber membrane. Scanning electron microscopy (SEM) showed the synthesized nanofibrous polystyrene (PS)/BCHMX sheets with clear and continual fiber were imaged with scanning electron microscopy (SEM). Characterization of the produced nanofiber was examined by Fourier Transform Infrared (FTIR), and X-ray diffractometer (XRD). Explosive sensitivity was also evaluated by both BAM impact and friction apparatus. Thermal behavior for the synthesized PS/BCHMX fiber and the pure materials were also investigated by thermal gravimetric analysis (TGA). The results show enhancement in the fabrication of nano energetic fibers with a size of 200–460 nm. The TG confirms the high weight percentage of BCHMX which reaches 60% of the total mass. PS/BCHMX fiber was confirmed with the XRD, FTIR spectrum. Interestingly, XRD sharp peaks showed the conversion of amorphous PS via electrospinning into crystalline shape regarding the applied high voltage. The synthesized PS/BCHMX nanofiber was considered insensitive to the mechanical external stimuli; more than 100 J impact energy and > 360 N initiation force as friction stimuli. PS/BCHMX is considering a candidate tool to deal with highly sensitive explosives safely and securely for explosives detection training purposes.