xPb(Zn 1/3 Nb 2/3 )O 3 –(1−x)PbZr 0.5 Ti 0.5 O 3 (xPZN–(1−x)PZT) (x=0.22–0.36) polycrystalline ceramics with finely varied PZN content were fabricated by a solid-state reaction method. The phase structure, microstructure and temperature dependence of the electrical properties were systematically investigated. The core of the morphotropic phase boundary (MPB) separating the tetragonal from rhombohedral phases located around the region with x=0.26–0.30, identified by XRD measurement and electrical properties. Higher PZN content favored rhombohedral symmetry and stronger relaxor-like characteristics. All compositions demonstrated well-saturated ferroelectric P–E loops, and a maximum remnant polarization of P r ~41.83μC/cm 2 with a corresponding coercive field E c ~11.3kV/cm was achieved around MPB. Optimum electrical properties of piezoelectric constant d 33 ~550pC/N, planar electromechanical coupling coefficient k p ~0.69, relative dielectric permittivity ε r ~2327 were obtained in the 0.28PZN–0.72PZT composition with a relatively high Curie point of T c ~325°C. This composition also possessed a good electric field-induced-strain property with d33⁎ up to 658pm/V (E=1kV/mm), making it promising for application in piezoactuators.