ZnO varistors are widely used in modern intelligent electrical equipment, and the preparation of miniaturized varistors with high voltage gradient has become a top priority. This work investigated the preparation of high voltage gradient ZnO–Cr2O3-based varistors doped with Er2O3 and analyzed the relationship between their microstructure and electrical properties. As the doping amount of Er2O3 increases from 0.00 to 0.75 mol%, Er2O3 phase obviously dissolving element Co distributed at the trigeminal grain boundaries increases, leading to the grain size d decreases from 3.16 to 1.70 μm, the nonlinear coefficient α increases from 6.22 to 50.48, the voltage gradient E1mA increases from 428.37 to 1616.76 V/mm, and the leakage current density JL decreases from 375.75 to 0.79 μA/cm2, achieving optimal comprehensive electrical performance of the sample with Er2O3 doping of 0.75 mol%, for which, the residual voltage ratios K reaches the minimum value of 1.14 under the impulse current density Jp of 63.7 A/cm2. When the doping amount of Er2O3 further increases to 1.00 mol%, the excessive Er2O3 phase aggregates at the trigeminal grain boundaries and distributes unevenly, leading to the growth of ZnO grains and performance deterioration of the samples. The ZnO–Cr2O3-based varistors have the advantages of much easier doping, and there is no dopant volatilization during the sintering process. This research provides an important reference for the development of high-performance, miniaturized ZnO–Cr2O3-based varistors.