Flexible nanocomposite films of poly(vinylidene fluoride)(PVDF)/nickel ferrite (NiFe₂O₄) fiber were made using solvent casting method. The NiFe₂O₄ fibers with a diameter of 400 nm were synthesized initially by means of electrospinnig technique. Studies of XRD and FTIR confirmed the formation of both α and β phases in the composite films. The presence of α-phase was diminished with the incorporation of NiFe₂O₄ and a maximum β-phase percentage (68%) was obtained. SEM and AFM analyses also demonstrated the transformation of the microstructures from α to β phase. The ferroelectric properties were tested with respect to NiFe₂O₄ loading and the composite film with 10 wt% NiFe₂O₄ exhibited a high P_max value of 1.46 μC/cm². VSM studies revealed the ferrimagnetic behaviour of the films and exhibited a maximum saturation magnetization value of 4.2 emu/cm³. Local ferroelectric properties were investigated through their domain switching behavior using dynamic contact electrostatic force microscopy (DC-EFM), and magnetic force microscopy (MFM) was used to analyze the magnetic properties. The magnetoelectric cross-coupling between ferroelectric and ferrimagnetic orderings is verified through the variations in ferroelectric parameters under different magnetic fields. Then a nanogenerator was fabricated using the composite films and generated an open circuit voltage of 10 V (peak-peak). Additionally, these films were made into magneto-mechano-electric (MME) generator, which could generate a 4.8 V (peak-peak) output voltage under a weak AC magnetic field of 10 Oe at 50 Hz.