BaCaxTiO3–0.04LiF (0.010 ≤ x ≤ 0.045) ceramics were prepared by normal sintering at 1100 °C in air. A two‐phase coexisted region across orthorhombic and rhombohedral symmetry was designed by refining the components. The detailed phase structure was analyzed quantitatively by the Rietveld refinement. BaCa0.035TiO3–0.04LiF ceramic showed better properties with d33 = 354 pC N−1, kp = 39%, Qm = 314, and TC = 65 °C, in which the relative proportion of rhombohedral symmetry was 74.86%, the grain size was 6.0 µm and the relative density was 91%, indicating that the synergistic effect of the phase structure, fine grain, and relatively high density contributed to the outstanding piezoelectric properties.