Nanofiber with porous structures were prepared by electrospray deposition (ESD) from poly(vinylidene fluoride) (PVDF)/poly(vinylpyrrolidone) (PVP) blend and subsequent selective removal of PVP. In the present work, the effect of blending ratio of PVDF/PVP on formation of the pore and crystal structure of residual PVDF fiber was investigated. The residual PVDF nanofiber showed a higher specific surface area (the highest specific surface area was 28.54 m2/g from PVDF/PVP = 67/33 w/w). The Fourier transform infrared spectroscopy and wide angle X-ray diffraction measurement also showed that selective removal of PVP enhanced the formation of β-phase crystal structure in PVDF nanofiber (β-phase content > 90%).Keywords: Electrospray Deposition, Nanofiber, Poly(vinylidene fluoride), Poly(vinylpyrrolidone), Selective Extraction, Porous Structure, Crystalline Structure