Polyvinylidene fluoride (PVDF) nanofiber mats prepared using electrospinning technique have been used for making mechanical-to-electrical energy conversion devices. However, the effect of residual charges on this energy conversion process has never been seriously considered yet. In this study, by removing residual charges from electrospun PVDF nanofiber mats using a solvent treatment method, the contribution of the charges to device energy harvesting performance was carefully examined. It has been found that isopropanol treatment could effectively remove most of residual charges from the nanofiber mats, without obviously affecting crystal structure of the fibers. The electric outputs decreased from 1.0 V and 1.2 μA to 0.45 V and 0.5 μA after the residual charges removal. It can be concluded that residue charges play an important role in mechanical-to-electrical energy conversion of electrospun nanofibers. The understanding obtained from this study may supply a strategy for enhancing electric outputs of piezoelectric devices in future. Copyright © 2017 VBRI Press.