Energy scavenging has been attracting the consideration of researchers in recent years. In this study, the fabrication and characterization of electrospun randomly oriented and aligned grooved polyvinylidene fluoride (PVDF) and poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE) fiber webs are studied. The fibers are generated with comparable diameters and the webs which are used as an active layer to directly make a piezoelectric nanogenerator are fabricated with the same thickness for accurate comparison. The results show that PVDF-TrFE fiber webs have better mechanical properties, crystallinity, and piezoelectric properties than PVDF fiber webs. Furthermore, the piezoelectric nanogenerator based on PVDF-TrFE fiber webs has higher electrical outputs than piezoelectric nanogenerator based on PVDF fiber webs owing to its high beta phase content (F(beta)). Moreover, the electrical outputs of the piezoelectric nanogenerator based on aligned fiber webs are higher than those based on randomly oriented fiber webs due to the increase in the friction area. We believe that our work can be served as a good reference for the comparison between the mechanical, physicochemical, and piezoelectric properties of PVDF and PVDF-TrFE fiber webs generated via electrospinning.