In this paper, the electrospinning technique has been employed to fabricate PVDF/CuO/Al nanocomposites, where the formulation was optimized on the basis of maximizing the reaction heat with increased efficiency. The graphene oxide (GO) has also been used as both lubricant and catalyst, which is well dispersed inside the PVDF matrix by the electrospinning process as well. It has been found that the smooth PVDF nano-fibers could be fabricated with GO content of 0.5 wt%, where the Al and CuO nanoparticles are also uniformly loaded. In comparison with the n-CuO/n-Al and PVDF/CuO/Al prepared by conventional mechanical mixing method, the GO-doped PVDF/CuO/Al nanocomposites via electrospinning improved heat of reaction, density as well as antioxidation capability. In addition, the electrospinning technique and doping of 0.5 wt% of GO can improve the reaction efficiency of PVDF/CuO/Al nanocomposites since they contribute to dispersion of components and homogeneous structure fabrication.