This research work reports on development and characterization of multi-walled carbon nanotube (MWCNT)-doped polyvinylidene difluoride (PVDF) nanofibers by the electrospinning method. PVDF is an extensively studied polymer both theoretically and experimentally due to its appealing ferroelectric, piezoelectric, and pyroelectric properties which strongly favors its promising applications in the development of micro/nanostructure devices. The foremost reason for its ferroelectric and piezoelectric behaviors has been attributed to its crystalline structure, specifically the presence of beta-phase; however, the existence of the small percentage of beta-phase in pristine PVDF limits its applications. To enhance the electroactive features in the PVDF, MWCNTs have been doped in it to prepare electrospun nanofibers, as electrospinning is a single-step approach. These nonwoven nanofibers were prepared at a DC voltage of 20 kV which were subsequently calcined at 100 degrees C for 12 h. The estimation of crystal structure and phase identification in these nanofibers have been determined by attenuated FT-IR and XRD, while the morphology, microstructure, mean diameter, and length have been examined by FE-SEM. The observed electrical conductivity, capacitance, permittivity (epsilon), conductivity (delta), and impedance (Z) in these samples have been tailored by doping a range of MWCNT contents and optimizing the experimental conditions.