Lead-free piezoelectric ceramics are strongly needed to replace the lead-based piezoelectric ceramics with increasing environmental concerns. Barium titanate (BaTiO3) systems are one of the most promising candidates due to excellent electrical properties. However, the sintering temperature for traditionally sintered BaTiO3 ceramics are about 1300°C, which restricts the applications of BaTiO3 ceramics. It is necessary to develop high piezoelectric properties of BaTiO3 based ceramics which are able to sinter at low temperature. The (Ba0.94Cax)Ti0.94Oδ-0.04LiF (x = 0.00 ~ 0.05 mol) ceramics were synthesized by a conventional sintering method at 1050°C. All the samples show high relative densities over 90%. X-Ray Diffraction pattern indicated that the crystallographic structure of the samples (x = 0.00 and 0.01 mol) are orthorhombic phase and changes to pseudocubic one with increasing Ca content to x = 0.03 mol. Two-phases with orthorhombic and pseudocubic symmetries coexisted at x = 0.02 mol, which contributes the excellent properties, in which the piezoelectric constant d 33 = 361 pC/N, the planar electromechanical coupling coefficient kp = 41.2%, the Curie temperature Tc = 70°C, the temperature of phase transition T O-PC = 34°C near the room temperature, the relative permittivity ε r = 4028 and the remanent polarization P r = 9.39 μC/cm2.