Composite nanofibers were prepared by electrospinning and thermal treatment from poly (vinylidene fluoride) (PVDF)-$SiO_2$ blend solution. The nanofibers were stacked on layers to produce fully interconnected pores. TEM micrographs and EDX spectra confirmed the presence of $SiO_2$ in the composite nanofibers. The porosity of nanofibers was effectively enhanced by the introduction of electrospinning technique. ATR-FTIR and XRD results revealed that PVDF in the composite nanofibers exhibited the mixture crystal structure of ${alpha}$-phase and ${eta}$-phase. The crystal structure of ${alpha}$-phase and crystallinity increased by the thermal treatment. In addition, the mechanical properties, thermal stability and hydrophobicity were markedly amplified by the thermal treatment.