Effect of calcination conditions on phase formation and particle size of lead zirconate (PbZrO3) powders synthesized by a solid-state reaction with different vibro-milling times was investigated. A combination of the milling time and calcination conditions was found to have a pronounced effect on both the phase formation and particle size of the calcined PbZrO3 powders. The calcination temperature for the formation of single-phase perovskite lead zirconate was lower when longer milling times were applied. The optimal combination of the milling time and calcination condition for the production of the smallest nanosized (similar to 28 nm) high purity PbZrO3 powders is 35 h and 750 degrees C for 4 h with heating/cooling rates of 30 degrees C/min, respectively.