It is shown that electrospun poly(vynilidene fluoride) nanofibers are fully poled right after preparation and show b-phase contents of 70%, therefore being able to be implemented into electroactive devices without further processing steps. Further,the local piezoelectric properties of individual electrospun fibers have been studied by piezoresponse force microscopy. Piezoelectric response, polarization switching, and nanoscale patterning of the fibers have been demonstrated. ; This work is funded by FEDER funds through the "Programa Operacional Factores de Competitividade – COMPETE" and by national funds arranged by FCT- Fundação para a Ciência e a Tecnologia, project references NANO/NMed-SD/0156/2007, PTDC/CTM/73030/2006 and PTDC/CTM/69316/2006. The authors also thank support from the COST Action MP1003, 2010 ‘European Scientific Network for Artificial Muscles’. V.S. thanks the FCT for the SFRH/BPD/63148/2009 grant, C. Ribeiro C. R. thanks the IINL for a financial support via a PhD grant and I. B. is thankful to FCT for the financial support via Ciência 2008 fellowship.