This study describes the doping effect of Yb2O3 on microstructure, electrical and dielectric properties of ZnO-V2O5- MnO2-Nb2O5 (ZVMN) ceramic semiconductors sintered at a temperature as low as 900°C. As the doping content of Yb2O3 increases, the ceramic density slightly increases from 5.50 to 5.54 g/cm3; also, the average ZnO grain size is in the range of 5.3-5.6 μm. The switching voltage increases from 4,874 to 5,494 V/cm when the doping content of Yb2O3 is less than 0.1 mol%, whereas further doping decreases this value. The ZVMN ceramic semiconductors doped with 0.1 mol% Yb2O3 reveal an excellent nonohmic coefficient as high as 70. The donor density of ZnO gain increases in the range of 2.46-7.41×1017 cm−3 with increasing doping content of Yb2O3 and the potential barrier height and surface state density at the grain boundaries exhibits a maximum value (1.25 eV) at 0.1 mol%. The dielectric constant (at 1 kHz) decreases from 592.7 to 501.4 until the doping content of Yb2O3 reaches 0.1 mol%, whereas further doping increases it. The value of tanδ increases from 0.209 to 0.268 with the doping content of Yb2O3.