In this article, a piezoelectric thin film was obtained by mixing polyvinylidene fluoride‐trifluoroethylene (P(VDF‐TrFE)) and barium titanate (BTO) via a solvent vaporization process. All the morphologies, crystal phases, thermal and electrical tests, as well as potential simulations by COMSOL, were studied to analyze sample performances. It has been demonstrated that BTO has a positive effect on increasing the piezoelectric functional phase‐β phase within P(VDF‐TrFE). Furthermore, the optimal ratio of BTO to P(VDF‐TrFE) was determined to be 10 wt%. BTO nanoparticles were evenly distributed in the P(VDF‐TrFE) substrate, forming a more directional structure. Based on the most suitable material composition, piezoelectric, and triboelectric nanogenerators were constructed to harvest mechanical energy from human motions. Moreover, the factors influencing the electrical outputs of nanogenerators were systematically studied, such as the force values and frequencies of excitation, as well as the piezoelectric layer materials. The applications of lighting LEDs highlighted the practical use in everyday life. Finally, the comparison between simulations, theoretical analysis, and experimental results demonstrated the effect of BTO in enhancing the overall material properties. This work expands the application potential of piezoelectric nanocomposites in energy collection and storage by designing and optimizing ceramic‐doped piezoelectric polymer composites.