The aim of this work is to study the effect of Nb element doping on the microstructure and electrical properties of lead zirconate stannum titanate (PZST) ceramic and to improve phase transition properties of PZST. Nb-doped Pb(Zr,Sn,Ti)O3 ceramic samples were prepared by the conventional mixed oxide method. Phase transitions induced by temperature, pressure, and electric field were measured with electric dielectric permittivity, hydrostatic pressure, and hysteresis. The microstructure of the samples was observed by electron scanning microscope to discuss the effect of Nb doping on PZST ceramics. The experiment results indicated that the remnant polarization (Pr), dielectric constant, phase transition, and microstructure were strongly dependent on Nb doping content.