The effects of silver addition on the sintering behavior, the dielectric, and ferroelectric properties of PMN-PNN-PZT piezoelectric ceramics for multilayer piezoelectric transformers were investigated. A small amount of silver promoted the sintering. but with more silver the density of the samples decreased. The silver incorporation affected the dielectric and ferroelectric properties of the samples. The dielectric constant presented an interesting change, and the dielectric loss increased slightly. The P-E loops indicated that the remnant (P-r) and saturated polarization (P-s) increased due to the silver addition with eventually enhanced ferroelectric properties. The degradation of the dielectric strength possibly restricted the polarizing conditions of multilayer piezoelectric devices.