In this work, it is shown that the electrospun poly(vynilidene fluoride) (PVDF) nanofibers have polymer chains re-oriented along the fiber axis and the beta-phase content reaches 72.7%, therefore being able to be implemented into electroactive device components. Further, nanoscale domain imaging and local piezoelectric coefficient d(33) of the nanofibers have been intensively studied using piezoresponse force microscopy (PFM). The piezoelectric response (PR) imaging and butterfly amplitude loop have been demonstrated to confirm that the nanodomains result from the out-of-plane displacement and the d(33) has an uneven distribution with the higher values on the fiber periphery.