In this study, neat polyvinylidene fluoride (PVDF) and its blend with polyoctafluoropentyl acrylate (POFPA) were electrospun under controlled conditions, and studied for their physico-mechanical and piezo-responsive behaviours. Initial FTIR studies confirmed the effect of thermal annealing on the crystalline phase transformations and chaindipole orientation in PVDF as a function of POFPA content. SEM data exhibited “root-shaped” morphology in the blend sample. Higher tensile strength (65.2±0.4 kPa) for the blend compared to that of neat PVDF (1.5±0.03 kPa) confirmed the elastic nature of the blend nanoweb. Peak-to-peak piezoelectric output signal (Vp-p 0.976 V) and capacitance hysteresis showed reduced tendency, whereas the capacitance maxima is higher for the blend sample (Cmax 0.182 nF) compared to that of neat PVDF (Vp-p 1.195, Cmax 0.147 nF). Overall, even 10 wt% addition of POFPA in PVDF greatly enhanced the tensile strength of nanofiber web along with improved piezocapacitive characteristics, a combination of great potential for many commercial sensor applications.