The effects of different nano-SiO2 contents on the rheological properties of poly(vinylidene fluoride) (PVDF) solution and mechanical, thermal, structural, and piezoelectric properties of composite nanofibers were investigated. Results showed an increase in fiber diameter (similar to 125 to 350 nm) and similar to 450% increase in tensile strength as the content of nano-SiO2 particles increased. The degree of crystallinity decreased by 19% as the nano-SiO2 content increased by 2% (w/w). Further investigation demonstrated that silica could significantly improve the piezoelectric properties of PVDF nanofibers as the output voltage showed an increase in the presence of silica attributed to change in the crystalline structure of PVDF.