TiO2-based varistor–capacitor ceramics co-doped with fixed Nb2O5, MnO2, Sm2O3 and various content of Sb2O3 are prepared, and then the effect of Sb2O3 on electrical properties of TiO2 varistor–capacitor ceramics is investigated. The results indicate that addition of Sb2O3 effectively decreases breakdown voltage (E1mA), while having less impact on the nonlinear coefficient (α). E1mA initially increases and then decreases with Sb2O3 increasing; contrarily, relative dielectric constant (εr) decreases first and then increases. It is found that composition of 98.3%TiO2-0.8%Nb2O5-0.3%MnO2-0.3%Sm2O3-0.3%Sb2O3 is obtained with a low breakdown voltage of 2.3 V/mm, nonlinear coefficient of 2.0, high relative dielectric constant of 7.6 × 104 and low dissipation factor of 0.25, which is consistent with the narrowest grain boundary barriers in the composition. The nonlinear coefficient initially increases and then decreases with increase of Sb2O3; it reaches a maximum value of 2.9 at 0.2 mol.% Sb2O3, which is consistent with the highest grain boundary barriers in the composition. In order to explain the nonlinear current–voltage characteristics, a grain boundary defect barrier model was introduced.