The out-of-plane piezoelectric response of PVDF nanofibers is much stronger than the in-plane. The polarization switching occurs at 20 Hz periodically with high sensitivity. The piezoelectric coefficient (d33) of the nanofibers is diameter-dependent. The thinnest nanofiber studied here is 30 nm and it has the maximal |d33| of 38.5 pm V−1.