Recently, piezo–tribo hybrid nanogenerators are developed using the synergistic effect. Exploration of multi-crystalline piezoelectric materials adds the advantage of mechanically to electrically converting hybrid systems. On the way, the multi-crystalline 0.3Ba0.7Ca0.3TiO3–0.7BaSn0.12Ti0.88O3 (BCST) materials are characterized by the structural, vibrational, and ferroelectric properties. The synergistic effect-based polydimethylsiloxane/BCST hybrid composite film is prepared for multi-energy harvesting. The triboelectric nanogenerator produces a maximum output voltage of 210 V. The hybrid device obtains the maximum output performance of 326 V. The harvested energy is used to charge commercial capacitors and power low-power electronics. The signal processing and analysis unit is constructed for monitoring or functioning in real-time finger movement. In the future, this kind of system can be coupled with augmented and virtual reality applications.