ZnO varistors were synthesized with ZnO powders and intensity milled composite additives as raw materials. The effect of milling time of the composite additives on the grain boundary phase distribution as well as the electrical properties was investigated in detail. The results show that ball milling composite additives have a significant effect on the ZnO varistors. The samples derived from ball milled composite additives possess the smaller size and more uniform distribution of the second phases, which improved the electrical properties obviously. The optimal ZnO varistor samples were obtained by ball milling 15 h for the composite additives, which possess average ZnO crystalline grain size of about 4 µm, the gradient voltage V1mA of 454 V/mm, the leakage current IL of 0.12 µA, and the nonlinear coefficient α of 55.