The high permeability Mn-Zn ferrites doped with CaO-Bi2O3-MoO3-XNb2O5 (X=0.000wt%-0.075wt%, step: 0.015%) were prepared by high temperature solid state reactions. The phase composition, microstructure and electromagnetic properties were characterized by XRD, SEM, FPP, impedance analyzer and soft magnetic AC testing system. The effects of Nb2O5 doping amount on the microstructure and electromagnetic properties of Mn-Zn ferrites were investigated. The results show that when a small amount of Nb2O5 is doped, Nb2O5 can refine the microstructure, improve the density, frequency stability and quality factor, electrical resistivity, and reduce the specific loss. When a large amount of Nb2O5 is doped, Nb2O5 will cause deterioration of microstructure and the electromagnetic properties of the Mn-Zn ferrites. When the Nb2O5 doping amount is 0.030wt%, the best comprehensive performance of the Mn-Zn ferrites is obtained.