The ferroelectric properties of sodium nitrite (NaNO2):poly(vinyl alcohol) nanocomposite films prepared by the solvent cast method have been studied. The optimization of the ferroelectric properties of the composite films as a function of the composition gave 50 wt % to be the optimum value. The enhanced remanent polarization was observed in the composite in the frequency range of 10 Hz–1 kHz. The stability of the ferroelectric polarization shows improvement over the pure NaNO2 films. The x-ray diffraction study revealed that the strain is reduced in the composite films. The images of field emission scanning electron microscope showed the nanosize and uniform distribution of particles in 50 wt % composite. The improved values of the polarization and stability have been attributed to the reduced strain in the composite. The ferroelectric phase transition peak was observed in the differential scanning calorimetry (DSC) scan. The ferroelectric phase transition temperature of the composite film obtained from the capacitance-voltage (C–V) measurements agrees well with the DSC measurements.