Nowadays, piezoelectric composites have attracted greatly significant interest in the field of bone tissue engineering. Polyvinylidene fluoride (PVDF) exhibits the highest piezoelectric properties among polymers and enables the fabrication of biocompatible, biodegradable, and hydrophilic scaffolds that reveal satisfactory mechanical, biological, and piezoelectric characteristics. The present study developed PVDF‐barium titanate (BT)/polyvinyl alcohol‐hydroxyapatite (HA) scaffolds with differing PVDF/PVA ratios through co‐electrospinning techniques. Comprehensive analyses of their physical, mechanical, and biological properties were conducted. The resulting scaffolds displayed a uniform, bead‐free morphology, comprising PVDF and PVA fibers containing BT and HA, respectively. Wettability, mechanical, and piezoelectric properties were estimated using a contact angle goniometer, tensile test, and piezometer. The addition of BT and HA improved the hydrophilicity of the final scaffolds. On the other hand, the addition of PVA slightly reduced the overall mechanical strength; however, this reduction was not statistically significant. Additionally, BT and HA enhanced the piezoelectric performance, while PVA contributed to a decrease in these properties. Among the fabricated composites, the PBT4‐PH20 (60‐40) exhibited superior wettability and piezoelectric characteristics alongside acceptable mechanical strength. In vitro evaluations indicated that this composite demonstrated enhanced biodegradability and bioactivity compared to the others, effectively supporting cell attachment, proliferation, and promoting calcium mineralization. Given these promising results, the PBT4‐PH20 (60‐40) composite has strong potential as a scaffold for bone regeneration applications.