Dielectric polyvinylidene fluoride (PVDF) and Barium titanate (BaTiO3)-PVDF nano-fibrous composites were made using the electrospinning process based on a design of experiments approach. An ultrasonication process was optimized using 2k factorial DoE approach to disperse BaTiO3 particles in PVDF solution in DMF. Scanning electron microscopy was used to characterize the microstructure of the fabricated mesh. The FT-IR and Raman analysis were carried out to investigate the crystal structure of the prepared mesh. Surface morphology contribution to the adhesive property of the composite was explained through contact angle measurements. The capacitance of the prepared PVDF-BaTiO3 nanofibrous mesh was a more than 40% increase over the pure PVDF nanofibers. The results obtained indicates that electrospinning offers a potential way to produce nanofibers with desired crystalline nature which was not observed in molded samples. In addition, BaTiO3 can be used to increase the capacitance, desired surface characteristics of the PVDF nanofibers which can find potential application as flexible piezoelectric sensor mimicking biological skin for use in structural health monitoring applications.