The goal of this research was to promote the bioactivity and osteogenic characteristics of polyvinylidene fluoride(PVDF) fibrous membrane, while preserving its piezoelectric property for bone regeneration. In this regard, core-shell fibrous membrane of PVDF-Ba0.9Ca0.1TiO3/polyvinyl alcohol(PVA) was developed via emulsion electrospinning approach. While PVA was in the outer layer of fibers with thickness of 53 +/- 18 nm, the Ba0.9Ca0.1TiO3 nanoparticles was uniformly dispersed in the PVDF core. The formation of PVA shell resulted in significant improvement of its hydrophilicity (3 times) and degradation rate, while piezoelectricity did noticeably modulate. In addition, incorporation of Ba0.9Ca0.1TiO3 nanopowder remarkably improved bioactivity, protein adsorption and mechanical properties of PVDF/PVA fibrous membranes. Finally, the osteogenic differentiation of mesenchymal stem cells on the nanocomposite fibrous membranes, in the absence of osteogenic supplements, was also observed. Overall, the results confirmed the promising potential of PVDF-Ba0.9Ca0.1TiO3/PVA fibrous membrane containing 1-2 wt% nanopowder for bone regeneration.