AbstractIn this work, the graphite nanopowder (GNP) reinforced poly(vinyl alcohol) based Bismuth ferrite (BiFeO3; BFO) composite films with different weight percentages of GNP using a solution casting technique. The electrical properties of GNP‐reinforced PVA composites are investigated using a complex impedance spectroscopy (CIS) technique to show the bulk and grain effect with the rise in frequency by an impedance analyzer in a frequency range from 102 to 106 Hz at room temperature. The single semicircle is showing in the complex planes using the real and imaginary impedance characteristics. The GNP‐reinforced PVA composite films show evidence of bulk and grain impact in complicated impedance analysis. Based on the Nyquist plot, it appeared that only the bulk effects of the resultant composite systems are present.