Microwave sintering is a novel and high efficiency sintering technology for ceramics, which exhibits many significant advantages, such as high rapid heating rate, energy saving and shorter sintering time, microstructures improvement, and lower sintering temperature. The 0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(0.55PNN-0.45PZT) piezoelectric ceramics by doping with Fe₂O₃ were prepared using the microwave sintering process at 1,200℃ for 2h. The effect of Fe₂O₃ doping on microstructure, dielectric and piezoelectric properties were investigated by using X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), impedance analyser, and ferroelectric tester in detail. The XRD results indicate that all samples possess typical pervoskite phase. In addition, both the piezoelectric and dielectric constants increases firstly and then decreases with increasing x. The optimum electrical properties of d₃₃=520pC/N, k_p=0.51, ε_r=4768, and tanδ=0.026 are obtained for the 0.55PNN-0.45PZT ceramics by doping with 0.8% Fe₂O₃.