(Ba1−xCax)(Ti0.92Sn0.08)O3 (x = 0.00–0.06 mol) ceramics with a high relative density over 96% were prepared by a conventional sintering method at 1480°C. At room temperature, a polymorphic phase transition from orthorhombic phase to tetragonal phase was confirmed by the XRD patterns in the composition range of 0.04 ≤ x ≤ 0.06. A high piezoelectric coefficient d33 up to 568 pC/N was obtained at x = 0.05 mol, which is higher than the other component of (Ba,Ca)(Ti,Sn)O3 system. At the same time, the corresponding planar electromechanical coupling factor kp, converse piezoelectric coefficient dS/dE, and dielectric constant εr reach 47.7%, 1013 pm/V, and 23000, respectively. These results indicate that the (Ba,Ca)(Ti,Sn)O3 ceramics are a promising candidate to replace for the lead-based piezoelectric materials.