The effect of Bi2O3‐B2O3‐SiO2‐ZnO glass (denoted as BBSZ) content on the densification, microstructure, and electrical properties of ZnO‐based multilayer varistors (MLVs) has been investigated. In ZnO‐based (MLVs), BBSZ acted as a promoter in ZnO grain growth, which increased the grain size of ZnO, resulting in a decrease in breakdown voltage. Results showed that the adding of BBSZ glass had an improvement in densification and overall properties of MLVs. It was found that a maximum value of 5.45 g/cm3 of the bulk density and the optimum properties (V1mA = 27.28 V, α = 40.33, IL = 0.75 μA, Ip = 35 A) of ZnO‐based MLVs were achieved with 3 wt% BBSZ glass sintered at 925°C for 3 hours.