A novel heterogenous precipitation method (H-P) combining the merits of solid state synthesis method (S-S-S) and the liquid routes was developed to synthesize the ZrO2 phase-free Zr-rich Pb0.99Nb0.02(Zr0.965Ti0.035)O-3 ceramics. The microstructure of the ceramics synthesized by H-P was more homogeneous and fine than that by S-S-S. The density, the dissipation factor, the ferroelectric properties and the dielectric breakdown of the ceramics synthesized by H-P are more outstanding than that by S-S-S. The dielectric breakdown (E (b)) increases markedly from 5 kV/mm to 6.5 kV/mm.