In this work, the grain growth behaviour of ZnO+V2O5(1 mol%)+Cr2O3(0.35 mol%)-based ceramics with 0.25–0.75 mol% additions of PrMnO3 was systematically investigated during sintering from 850°C to 925°C with the aim to control the ZnO grain size for their application as varistors. It was found that with the increased addition of PrMnO3, not only did the average grain size decrease, but the grain size distribution also narrowed and eventually changed from a bimodal to unimodal distribution after a 0.75 mol% PrMnO3 addition. The grain growth control was achieved by a pinning effect of the secondary ZnCr2O4 and PrVO4 phases at the ZnO grain boundaries. The apparent activation energy of the ZnO grain growth in these ceramics was found to increase with increased additions of PrVO4; hence, the observed reduction in the ZnO grain sizes.