Development of flexible piezoelectric nanogenerator (PENG) is a real challenge for the next-generation energy-harvesting applications. In this paper, we report highly flexible PENGs based on poly(vinylidene fluoride) (PVDF)/2 wt % Ce-FeO and PVDF/2 wt % Ce-CoO nanocomposite fibers. The incorporation of magnetic Ce-FeO and Ce-CoO greatly affects the structural properties of PVDF nanofibers, especially the polymeric β and γ phases. In addition, the new composites enhanced the interfacial compatibility through electrostatic filler-polymer interactions. Both PVDF/Ce-FeO and PVDF/Ce-CoO nanofibers-based PENGs, respectively, produce peak-to-peak output voltages of 20 and 15 V, respectively, with the corresponding output currents of 0.010 and 0.005 μA/cm under the force of 2.5 N. Enhanced output performance of the flexible nanogenerator is correlated with the electroactive polar phases generated within the PVDF, in the presence of the nanomaterials. The designed nanogenerators respond to human wrist movements with the highest output voltage of 0.15 V, for the PVDF/Ce-FeO when subjected to hand movements. The overall piezoelectric power generation is correlated with the nanoparticle size and the existing filler-polymer and ion-dipole interactions.