In this work, Ba1−xCaxTi0.88Zr0.12O₃ (x= 0.00–0.25) ceramics were prepared by a solid-state reaction method, and the variation of dielectric, ferroelectric and piezoelectric characteristics has been investigated together with the structure evolution. The crystal structure varies from rhombohedral to tetragonal at room-temperature and the morphotropic phase boundary (MPB) is determined around x= 0.10, where the significantly enhanced ferroelectric and piezoelectric properties are achieved. With the increase of Ca content, the system gradually evolves into a relaxor ferroelectric. This work provides useful guidance for future research on lead-free piezoelectric materials.In this work, Ba1−xCaxTi0.88Zr0.12O₃ (x= 0.00–0.25) ceramics were prepared by a solid-state reaction method, and the variation of dielectric, ferroelectric and piezoelectric characteristics has been investigated together with the structure evolution. The crystal structure varies from rhombohedral to tetragonal at room-temperature and the morphotropic phase boundary (MPB) is determined around x= 0.10, where the significantly enhanced ferroelectric and piezoelectric properties are achieved. With the increase of Ca content, the system gradually evolves into a relaxor ferroelectric. This work provides useful guidance for future research on lead-free piezoelectric materials.