A highly sensitive flexible piezoelectric material is developed by using a composite nanofibers web of polymer and metal. The nanofibers webs are made by electrospinning a mixed solution of poly(vinylidene fluoride) (PVDF) and silver nanowires (AgNWs) in the co-solvent of dimethyl formamide and acetone. SEM images show that the obtained webs are composed of AgNWs doped PVDF fibers with diameters ranging from 200nm to 500nm. Our FTIR and XRD results indicate that doping AgNWs into PVDF fiber can enhance the contents of beta phase of the PVDF. UV-Vis spectrum shows a slightly red shift at 324 nm and 341 nm after the AgNWs doping into PVDF, proving the presence of interaction between AgNWs and the PVDF polymer chain. The piezoelectric constant d33 of the nanofibers webs tested with a homemade system, reveals a good agreement with FTIR and XRD characteristic, and the highest one is up to 29.8 pC/N for the nanofibers webs containing 1.5% AgNWs, which is close to that of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE), 77/23). This study may provide a way to develop high-performance flexible sensors.