The microstructure and electrical properties of 0.02Pb[Cd1/2W1/2)O3-0.505PbZrO3-0.475PbTiO3 with MnO2 addition have been investigated. The amount of MnO2 addition was 0, 0.2, 0.4, 0.6, 0.8, 1wt%, respectively. When MnO2 is added up to 0.2wt%, Mn3+ which is substituted for Ti4+ site make hole and act as a acceptor. When MnO2 is added over 0.2wt% Mn3+ which is substituted for Cd2+ site create electron and act as a donor. The variation of grain size show that it was rapidly increased by 0.4wt% addition of MnO2, and while that in the range of over 0.6wt% addition of MnO2 it was decreased. The solid solution range of MnO2 that assumed in this composition according to the variations of microstructure and electrical properties was 0.4-0.6wt%.