Iron sand-based Fe3O4 nanoparticles–polyvinylidene fluoride (PVDF) nanofibers were processed inside an electrospinning system at room temperature. The incorporation of Fe3O4 nanoparticles into the PVDF matrix decreases the diameter of the fibers. The presence of the Fe3O4 crystalline phase in the electrospun PVDF-Fe3O4 fiber indicates the unchanged Fe3O4 crystal structure. The surface morphology of the samples was altered considerably after the electrospinning and heating processes. Infrared spectroscopy identification confirmed the PVDF α to β-phase transformation in the PVDF and PVDF-Fe3O4 fibers. The thermal analysis detected a higher residual mass of the PVDF-Fe3O4 sample than that of the pure PVDF at high temperatures. Through the hysteresis characteristics, a ferromagnetic behaviour was observed for all samples. The efficient and low-cost fabrication of the PVDF-Fe3O4 fibers could be considered practical for diverse applications of nanotechnology.