Piezo- and ferroelectric nanofibers of the polymer poly(vinylidenefluoride) (PVDF) have been widely employed in strain and pressure sensors as well as nanogenerators for energy harvesting. Despite this interest, the mechanism of electromechanical transduction is under debate and a deeper knowledge about relevant piezoelectric or electrostatic properties of nanofibers is crucial to optimize transduction efficiency. Here poly(vinylidenefluoride-trifluoroethylene) nanofibers at different electrospinning conditions are prepared. Macroscopic electromechanical response of fiber mats with microscopic analysis of single nanofibers performed by piezoelectric and electrostatic force microscopy are compared. The results show that electrospinning favors the formation of the piezoelectric beta-phase in the polymer and leads directly to piezoelectric properties that are comparable to annealed thin films. However, during electrospinning the electric field is not strong enough to induce direct ferroelectric domain polarization. Instead accumulation of triboelectric surface charges and trapped space charge is observed in the polymer that explain the electret like macroscopic electromechanical response.