With a cylindrical shock-wave-loading technique, the single perovskite-phase Pb(Zr0.95Ti0.05)O3 powders (PZT 95/5) were synthesized by shock-induced chemical reactions in heterogeneous multi-material powder mixtures of Pb3O4, ZrO2 and TiO2. The phase and crystal structure of as-synthesized powders were characterized by X-ray diffraction (XRD) and fourier transform infrared (FT-IR) analysis. And the microstructure and electrical properties of PZT 95/5 ceramics prepared with as-synthesized PZT powders at different sintering temperature were analyzed. The results showed that the shock-wave-induced a large quantity of lattice defects and distortion of the crystal structure in the shock-synthesized PZT powders, which could enhance the sintering activity. Thus, the optimal density and electrical properties of PZT ceramics prepared with as-synthesized powders could be obtained at a sintering temperature of 1200–1225 °C for 3 h, significantly lower than the sintering temperature of PZT 95/5 ceramics prepared by conventional solid-state reaction.