Piezoelectric nanosensors were prepared with a novel type of dehydrofluorinated poly(vinylidene fluoride) (PVDF) nanofibrous membrane. With the synergistic effect of the dehydrofluorination reaction and applied high voltage electric field, the piezoelectric and energy storage properties of fibrous membranes attained great improvement. It was found that the simultaneous introduction of conjugated double bonds to the backbone of PVDF which was accompanied with the elimination of HF, resulted in the decrease of its molecular weight, solution viscosity and hydrophobicity. The crystalline phase, diameter, piezoelectric and energy storage properties of electro-spun PVDF nanofiber membranes significantly depend on the degree of HF elimination in dehydrofluorinated PVDF. The dehydrofluorinated PVDF with 5 hours of reaction exhibits the highest discharged energy density (W_rec) and energy storage efficiency (η), but excessive dehydrofluorination reaction is unfavorable to the energy storage properties. In addition, the dehydrofluorinated PVDF fiber membrane-based nanosensor possesses a larger electrical throughput (open circuit voltage of 30 V, which is three time that of the untreated PVDF), indicating that the introduction of double bonds can also improve the piezoelectric properties of PVDF nanofibers.