xPb(Yb1/2Nb1/2)O3-(1 − x)Pb(Zr0.36Ti0.64)O3 (xPYN-(1 − x)PZT) piezoelectric ceramics were prepared by the conventional ceramic processing via a B-site oxide mixing route. The synthesized xPYN-(1 − x)PZT ceramics exhibit majority of perovskite structure with slight content of impurity, which exhibit typical tetragonal structure with slight orthorhombic distortion depending on compositions. All the xPYN-(1 − x)PZT ceramics exhibit high Curie temperature (TC/Tm), higher than 380 °C, and their dielectric behavior above TC/Tm can be fitted well by the Curie-Weiss law. The xPYN-(1 − x)PZT ceramics exhibit large resistivity, and excellent ferroelectric and piezoelectric properties, which provide promising for the high-power and high-temperature piezoelectric applications. However, electric energy density of the xPYN-(1 − x)PZT ceramics is small due to their nearly rectangular shape of polarization-electric field (P-E) hysteresis loop and early electric displacement saturation, which is not suitable for high energy and power storage applications.