<p>The demand for highly efficient and mechanically flexible materials is increasing rapidly, as conventional piezoelectric materials often exhibit brittleness and low energy-conversion efficiency. In the present study, Ce-doped ZnO (Ce: ZnO NPs) with concentrations of 5% and 10% were synthesized through the sol–gel method and incorporated into polyvinylidene fluoride (PVDF) membranes using an ultrasonication-assisted dispersion technique. The structural analysis showed that pure PVDF exhibits a crystalline β-phase, whereas composite membranes (PVDF/Ce: ZnO-5 and PVDF/Ce: ZnO-10) have a bi-phasic structure containing the electroactive β-phase of PVDF and the stable hexagonal wurtzite phase of Ce: ZnO NPs. SEM micrograph showed that there is a porous nature in pristine PVDF, and the porosity starts decreasing with an increase in Ce: ZnO loading in the PVDF matrix. XPS analysis confirms the successful incorporation of Ce into the ZnO lattice with mixed Ce³⁺/Ce⁴⁺ states, accompanied by the formation of oxygen vacancies. The remanent polarization (P_r) showed a remarkable rise from 0.041 μC/cm² (PVDF) to 0.11 μC/cm² (PVDF/Ce: ZnO-10), and the piezoelectric coefficient (<InlineEquation ID="IEq1"> <EquationSource Format="TEX">\({d}_{33}\)</EquationSource> <EquationSource Format="MATHML"><math> <msub> <mi>d</mi> <mn>33</mn> </msub> </math></EquationSource> </InlineEquation>) increased from 27 pC/N to 79 pC/N correspondingly. These results show the improved electromechanical coupling behavior and energy harvesting potential of flexible PVDF/Ce: ZnO composite membranes for a futuristic approach in fabricating nanogenerators and wearable energy harvesting systems.</p>