To enhance the electrical properties and Curie temperature of lead-free piezoelectric materials, polycrystalline Ba0.85Ca0.15Zr0.1Ti0.9O3–xCa0.28Ba0.72Nb2O6 (BCZT–xCBN) ceramics were synthesized by solid-state reaction. X-ray diffraction analysis of the ceramics revealed that the crystal structure changed from orthorhombic to tetragonal, with an increase in CBN content. The Curie temperature was improved from 91°C to 98°C and favorable electrical properties (d33~590pC/N, kp~0.46) were obtained for the BCZT-0.2mol% CBN ceramics, along with high remnant polarization (Pr=12.5 μC/cm2), and a low coercive field strength (Ec=1.5kV/cm). The ceramics also exhibited good dielectric temperature stability over a wide temperature range.