Bi(Zn0.5Ti0.5)O3 (BZT)-modified Pb(Zr1−ξTiξ)O3 (PZT) single crystals have been grown using a top-seeded solution growth technique and characterized by various methods. The crystal structure is found to be rhombohedral by means of X-ray powder diffraction. The composition and homogeneity of the as-grown single crystals are studied by laser ablation inductively coupled plasma mass spectrometry and X-ray photoelectron spectroscopy. The domain structure of a (001)cub platelet is investigated by polarized light microscopy (PLM), which confirms the rhombohedral symmetry. The paraelectric-to-ferroelectric phase transition temperature TC is found to be 313°C with the absence of rhombohedral–tetragonal phase transition. The ferroelectric properties of the ternary crystals are enhanced by the BZT substitution with a remanent polarization of 28 μC/cm2 and a coercive field EC of 22.1 kV/cm.