The effect of Cr2O3 on the electrical properties of the multicomponent ZnO varistors was investigated using voltage-current curves and impedance spectroscopy. The structure and morphological modifications were analysed by X-ray diffraction and scanning electron microscopy, respectively. It was observed in samples with addition 0.1 mol% Cr2O3 that there was an improvement in the electrical properties of the varistors, but the increase in concentration had a deleterious effect on the potential barrier at the grain boundary. The excess Cr2O3 segregates at the grain-boundary region and increases the donor concentration, leading to a higher leakage current.