In the present work, lead-free (Ba_1−xCa_x)(Zr_0.04Ti_0.96)O₃ (x=0.00–0.09) ceramics were fabricated via a solid-state reaction method. The microstructure and electrical properties of the ceramics were investigated. The microstructure of the BCZT ceramics showed a core shell structure at compositions of x=0.03 and 0.06. The substitution of small amount of Ba²⁺ by Ca²⁺ resulted in an improvement of the piezoelectric, dielectric and ferroelectric properties of the ceramics. The orthorhombic–tetragonal phase transition was found in the composition of x≤0.03. Piezoelectric coefficient of d₃₃∼392 pC/N and lowest E_c∼3.3 kV/cm with highest P_r∼14.1 μC/cm² were obtained for the composition of x=0.03 while its Curie temperature (T_C) was as high as 125 °C. However, the ferroelectric to paraelectric transition temperature had slightly shifted towards room temperature with increasing Ca²⁺ concentration.