A single stage electrospinning process can give rise to preferentially oriented induced dipoles in poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] nanofibers. The piezoelectricity of as-electrospun P(VDF-TrFE) nanofiber webs opens up new possibilities for their use as a flexible nanogenerators and nano-pressure sensors. In this work, the origin of the piezoelectricity has been spotlighted by randomization of the induced dipoles at the Curie temperature and analyzed by polarized FT-IR spectroscopic techniques as well as by detecting the piezoelectric signal from a nano-pressure sensor.