A novel approach to preparing electrospun polyvinylidene fluoride (PVDF) nanofibers is proposed, with high piezoelectric performance. PVDF nanofibers are doped with inorganic salts without the use of any postpolarization treatment. Twenty‐six salts are doped into the nanofibers and their piezoelectric properties are studied. The salts are classified into three groups based on their differing piezoelectric enhancement effects. A piezoelectric nanogenerator fabricated with an optimized electrospun PVDF nanofiber mat shows a piezovoltage seven times greater than that of a device based on undoped nanofibers. The simple and low‐cost approach to fabricate these piezoelectric nanofiber mats may broaden the range of industrial applications of these materials in energy‐harvesting devices and portable sensors.