The effects of polyvinylidene fluoride (PVDF) wt. % and electric fields on the production of PVDF fibers using a novel centrifugal electrospinning design were investigated. High-quality, bead-free fibers with diameter of (0.55 ± 0.04) μm were successfully produced. Fibers with exceptionally high β-phase content of 96.1 % and piezoelectric coefficient, d33 of (−157 ± 5) pC N−1 were obtained using PVDF amount and electric field of 14.0 wt % and 400 V cm−1, respectively. Under 3.0 N repetitive vertical forces, the fabricated piezoelectric nanogenerator (PENG) exhibited impressive open-circuit voltage, short-circuit current and power density of (32.6 ± 0.7) V, (3.26 ± 0.07) μA and (15.4 ± 0.6) μW cm⁻2, respectively. The production of high and well aligned β-phase in the fibers indicated by good d33 values are the likely reasons for the excellent performance of the PENG. Ultimately, potential of the fabricated PENG as a self-power supply for low-energy electronic devices was demonstrated.