New binary system (1−x) PbTiO3−xBi(Ni1/2Zr1/2)O3 (PT–100x BNZ) with x ≤ 0.45 were synthesized via solid-state reaction route. A morphotropic phase boundary (MPB) was identified around x = 0.40 by X-ray diffraction (XRD) method. The ceramics with MPB composition exhibit enhanced ferroelectric properties. A large piezoelectric coefficient (d33) up to 400 pC/N was obtained for the PT–40BNZ, which is comparable with the PbTiO3–BiScO3 (PT–BS, 450 pC/N).The frequency dependence of dielectric permittivity of PT–40BNZ shows characteristic of a strong relaxor feature and a transition temperature around 290°C (1 MHz). Temperature effect on the unipolar strain was also investigated. The present system with high d33 is a competitive piezoelectric material, as no expensive oxide is used here compared with the PT–BS.