Being capable of interconverting electrical and mechanical energy, piezoelectric materials are essential for electromechanical devices. In this study, high-performance 0.95Pb(Zr0.52Ti0.48)O3–0.05Pb(Mn1/3Nb2/3)O3 (PZT-PMnN) piezoelectric ceramics were prepared by spark plasma sintering (SPS). We systematically investigated temperature-dependent electrical properties and phase structure of ceramics. The SPS temperature was found to be optimized at 950 °C. PZT-PMnN ceramic sintered at 950 °C possessed high piezoelectric performances, i.e. d33 of 411 pC/N and d33* of 556 pm/V. Furthermore, a high mechanical quality factor Qm (480) and low dielectric loss (0.19%) were obtained. Therefore, the spark-plasma-sintered PZT-PMnN ceramic is a promising candidate for applications.