In recent years, the exploration of ways to enhance flexible piezoelectric sensors through the use of nanofillers and electrospinning has garnered significant attention. This paper presents the development of lead-free flexible piezoelectric sensors based on polyvinylidene fluoride (PVDF)/K0.5Na0.5NbO3 (KNN), augmented with bismuth chloride to further promote the formation of the PVDF beta-phase and enhance its conductivity. The sensor was fabricated via electrospinning, with KNN synthesized through a hydrothermal reaction at 180 degrees C. Fourier transform infrared spectroscopy and x-ray diffraction were employed to characterize the beta-phase content and crystallinity of the PVDF-based flexible piezoelectric sensors. The results revealed that the piezoelectric composite film containing 2 wt.% BiCl3 and 2 wt.% KNN exhibited the optimal piezoelectric phase, significantly enhancing its piezoelectric performance. Subsequently, four types of nanofiber-based piezoelectric sensors [PVDF, PVDF/KNN (KP), PVDF/BiCl3 (BP), and PVDF/BiCl3/KNN (BKP)] were analyzed to systematically explore the factors influencing the flexible piezoelectric sensors. It was observed that with the incorporation of fillers, the voltage output progressively increased from the original (V = 0.41 V, I = 5.90 nA) to BKP (V = 5.89 V, I = 54.94 nA). Ultimately, the developed BKP was applied to various parts of the human body, generating output voltages of 2.1 V, 3.6 V, 4 V, and 0.32 V at the elbow, knee, neck, and throat, respectively, when stretched at specific angles, thereby demonstrating its practical applicability.