<p>Poly vinylidene fluoride (PVDF) is blended with poly (vinylidene fluoride-co-hexafluoro propylene) (PVDF-HFP) <i>via</i> solution-casting technique. Herein, various concentrations of <i>ex-situ</i> synthetic ceria nanoparticles (CeO₂NPs) were incorporated within a (50/50 wt% PVDF/PVDF-HFP) polymeric blend (PB). The prepared ceria nanocomposites were characterized by X- ray diffraction (XRD), Scanning electron microscope (SEM), Fourier transformed infrared (ATR-FTIR) and UV/Vis analysis. XRD and FTIR analysis confirmed that the crystalline electroactive β-phase in the PVDF and PVDF-HFP is enhanced after blending and doping with CeO₂NPs. UV/Vis analysis showed that both direct and indirect band gaps for nanocomposites films are reduced to be about 3.37 and 3.2&#xa0;eV, respectively. Thermally stimulated depolarization current (TSDC) measurement of the different relaxation phases with polarization in the corona discharge field for different prepared samples had been obtained. TSDC results of the main β-relaxation peak show an enhancement of the relaxation time (τ) and decrease in activation energy (E_a), which is related to higher regularity of the system structure. The piezo- and pyroelectric activity of the various prepared samples were investigated. Pyroelectric coefficient enhanced to be about ≈ 68.5 µC/m²K for 20wt.% CeO₂/PB. The high piezoelectric coefficient d₃₃ obtained for 20wt.% CeO₂/PB was about 37.2 pC/N. This innovative flexible piezoelectric structure emerges as a strongly favorable candidate that can be applied as intelligent stress-responsive materials utilized in various energies harvesting piezoelectric technologies.</p>