The polyvinylpyrrolidone (PVP)/poly(vinylidene fluoride) (PVDF) core-shell nanofiber mats with superhydrophobic surface have been prepared via electrospinning its homogeneous blending solutions, and the formation of the core-shell structure was achieved by the thermal induced phase separation assisted with the low surface tension of PVDF. The electrospinnability of the blending solutions was also investigated by varying the blending ratio of the PVP and PVDF, and it enhanced with the increase of PVP content. SEM and TEM results showed that the fibers size was varied in the range of 100 nm-600 nm with smooth surface and core-shell structure. The composition of the shell layer was determined by the XPS analysis, and further confirmed by water contact angle (WCA) testing. As the fraction of PVDF exceeding PVP in the electrospinning solutions, the nanofiber mats showed superhydrophobic property with the WCA above 120 degrees. It indicated that the PVDF was concentrated in the shell layer of the fibers. X-Ray diffraction (XRD) and attenuated total reflection infrared spectroscopy (ATR-IR) analysis indicated that the PVDF was aggregated with the beta-phase crystallite as dominant crystallite. The nanofiber mats with the gas breathability and watertightness ability due to the porous structure and superhydrophobic would be potential applied in wound healing. (C) 2014 Published by Elsevier Ltd.