A two-step synthesis method was used to prepare a flexible PVDF/ZnFe₂O₄ multiferroic nanocomposite film. ZnFe₂O₄ nanofibers synthesized using electrospinning technique were incorporated into a PVDF matrix to form PVDF/ZnFe₂O₄ composite films through the solution-casting process. XRD patterns confirmed the formation of the polar β-phase in films, which is responsible for ferroelectricity. The percentage of the β-phase, calculated by FTIR analysis, reached 88% with the incorporation of ZnFe₂O₄ in PVDF. The transformation of α to β-phase microstructure were examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The dielectric constant and tangent loss of the composites with respect to ZnFe₂O₄ loading were measured. The dielectric constant increase with the increasing concentration of ZnFe₂O₄, and a maximum value of 30 was obtained for a ZnFe₂O₄ concentration of 15 wt%. Ferroelectric properties were analyzed by taking into consideration the domain switching behavior, which was investigated by dynamic contact electrostatic force microscopy (DC-EFM), whereas the magnetic properties were analyzed using magnetic force microscopy (MFM). The as-synthesized composite films were further used to fabricate a nanogenerator, which was capable of generating up to 7 V (peak–peak) as a maximum open circuit voltage for a 15 wt% ZnFe₂O₄-loaded film at 1.5 N of applied force. In addition, the nanogenerator delivered an output power of 4 μW at a load resistance of 500 kΩ, and the results were compared with previous results.