ZnO-based varistors consisting of 96 mol% ZnO and 4 mol% additive oxides (Bi₂O₃, Sb₂O₃, NiO, Co₂O₃, MnO and Cr₂O₃) have been prepared. Four different procedures have been applied to obtain the starting powder mixture. Three of the procedures involve sol–gel processing of the additive oxide mixture, and in two cases the surface of the ZnO grains has been covered by the additive oxides. The microstructural and phase composition development during the sintering process has been monitored and the electrical properties of the varistors have been determined. Higher breakdown voltages are obtained for varistors produced by sol–gel-processed starting materials, and the highest values are found for varistors prepared from ZnO grains covered with the additive oxides. Phase analysis revealed that the spinel phase, which retards the grain growth of the ZnO particles, is formed at lower temperatures and in larger amounts in these compacts. The higher breakdown voltages of these compacts thus seem to be related to the content of more finely grained ZnO particles in these compacts.