(Ba_1−xLa_x)(Ti_1−x/2Ca_x/2)O₃ (0.03 ⩽ x ⩽ 0.06) (BLTC) ceramics were prepared using a mixed oxides method. The structure, microstructure, and dielectric properties of BLTC were investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, atomic force microscope, and dielectric measurements. Both symmetric (2 0 0) XRD peak indicative of cubicity and sharp 308 cm⁻¹ Raman band indicative of tetragonality are characteristics of pseudo-cubic symmetry of BLTC. The unit cell volume of BLTC increased linearly with x, satisfying Vegard’s law. A strong “Raman charge effect” appeared at 836 cm⁻¹ because of the aliovalent double substitution in BLTC. The x = 0.03 sample because of its higher permittivity (ε′ = ∼2000) and lower loss (tan δ < 0.04) is a novel dielectric for X7R applications. The formation of defect complexes was responsible for the dielectric-temperature stability of BLTC.