The electrical properties of (Nb, Li)-doped SnO2 ceramics as a new varistor material were investigated. The sample 97.95%SnO2@0.50%Li2O.0.05%Nb2O5 (mol fraction) sintered at 1450℃ possess the highest density (p=6.77 g/cm3)and nonlinear electrical coefficient (α=11.6). The substitution of Sn4+ with Li+ increases the concentration of oxygen vacancies, together with the formation of solid solution, which will increase the sintering rate greatly and decrease the optimized sintering temperature. The substitution of Sn4+ with Li+ and the variation of temperature play very important effects on the densities, dielectric constant, nonlinear electrical properties and other characteristics of the samples. The properties of the grain boundary barrier and the microstructural characteristics were investigated to ensure the effect of the dopants and the temperature. A grain boundary defect barrier model was used to illustrate the grain boundary barriers formation in SnO2-Li2O-Nb2O5 varistors.