The effects of the electrical degradation characteristics and microstructure of Sb2O3-doped ZnO varistors were investigated by optical microscopy, X-ray diffraction (XRD) analysis, and voltage-current (V-I) characteristics analysis. The nonlinearity index α of the V-I characteristics of the Bi-Mn-Co-Sb2O3-doped ZnO varistors decreased with increasing Sb2O3 content after electrical degradation. The twin crystal of ZnO was formed by doping with Sb2O3. The number of twin crystals, of which two c-axes are perpendicular to the twin plane, increased and the number of twin crystals, of which c-axes are parallel to the twin plane, decreased with increasing amount of Sb2O3 doped. It is suggested that electrical degradation is affected by the combination of the orientation of ZnO grains containing twin planes and a double Schottky barrier may not be formed in the twin plane.