Environment-friendly piezoelectric micro/nanogenerators have attracted tremendous attention due to the increasing demand for portable self-power devices. Here, the [(0.94−x)Bi0.5Na0.5TiO3–0.06BaTiO3–xK0.5Na0.5NbO3; BNT-BT-xKNN] lead-free ceramic, at x = 0, 0.02, 0.04, 0.06, 0.08 and 0.10 mol%, was prepared via the solid-state method. The doping concentration x = 0.02 mol% shows the highest dielectric properties and the lowest dielectric loss. The active layer of the hybrid device is made by mixing BNT-BT-2KNN into the PDMS to form a series of polymer-ceramic composite films ranging from 7 to 19 wt% of BNT-BT-2KNN. The electrical response of the composite film is systematically studied with the addition of different weight percentages of the particles to the PDMS matrix. It was found that incorporating BNT-BT-2KNN at 11 wt% into the PDMS matrix exhibited the optimum harvesting performance, resulting in an output voltage and current density of about 30 V and 0.28 μA/cm2, respectively. The hybridized PENG and TENG devices could operate in a long-term cyclic mode, charge the capacitor for energy storage, and also light up LEDs. This research proposed a simple device fabrication and provided a guideline for the development of high-performance microgenerators, which is crucial for device development and practical use in the future.