The effects of high energy ball-milling (HEBM) on the sintering behavior and piezoelectric properties of 0.1 wt% doped 0.8Pb()-0.2Pb() (PMN-PZT) ceramics were investigated. It was found that HEBM treatment was quite effective to reduce the average particle size down to 300 nm, leading to increased density as well as enhanced piezoelectric properties of a sintered specimen even though prolonged HEBM resulted in unwanted secondary phases that caused a degradation of piezoelectric properties. The dielectric constant (), piezoelectric coupling factor () and piezoelectric constant of 0.1 wt% doped PMN-PZT ceramics prepared via HEBM for 10 h reached 2040, 0.68 and 554 pC/N, respectively.