Abstract: To prepare nanofibers with good piezoelectric properties and explore the impact of electrical signals triggered by mechanical signals on cell behavior, polyvinylidene difluoride/polyvinyl pyrrolidone/barium titanate (PVDF/PVP/BT) piezoelectric functional nanofibers were prepared by electrospinning blending. The contact angle of PVDF/PVP fiber was 113.47°. After adding BT and further plasma treatment, the contact angle decreased to 90.43°. The addition of BT particles can induce the transformation of the phase in PVDF. When the BT content was 20%, the beta phase content can reach as high as 53.86%. Additionally, due to the rigidity of BT, the Young's modulus of PVDF/PVP/BT fibers increased with the increase of BT content. Due to the synergistic effect of BT and PVDF on piezoelectric signals, the output voltage reached 0.133 V as the BT content increased to 20%. After 5 days of ultrasonic treatment and cultivation, the activity of human umbilical vein endothelial cells (HUVECs) on PVDF/PVP/20%BT fiber increased by 2.6%. Nanofibers with higher electrical properties were beneficial for the adhesion and proliferation of HUVECs. Therefore, PVDF/PVP/BT nanofibers with good piezoelectric properties are expected to be applied in vascular tissue engineering.