Polycrystalline nano-grain-boundary multi-doping ZnO-based nonlinear varistors with higher concentration additives have been fabricated by sol-gel and standard solid-state reaction method, of which the best sample has a very high threshold voltage of E-b = 3300 V/mm. The effect of sintering processes, sintering temperature and sintering time, and that of additive concentration of Bi2O3 on E-b of the samples are systematically investigated. The results show that the great merit of sol-gel method is its high threshold voltage obtained by a lower sintering temperature than the solid-state reaction method. The present work also shows that five phases including solid-state sintering, rich Bi liquid phase formation and ZnO as well as other additive dissolution, ZnO grain growth, the secondary phase sufficient formation and evolution have been experienced at different sintering temperatures. The hole type defect and nonhomogeneity of the microstructure will lead to the decrease of threshold voltage, i.e., the grain size and the homogeneity of the material will be important factors and directly affect the characteristic of the varistor. The sintering characteristic and the influence of Bi2O3 content on the threshold voltage are also discussed. (c) 2004 Elsevier B.V. All rights reserved.