Ba_1−xCa_xTi_0.9Zr_0.1O₃ (x = 0.10, 0.15, 0.18) solid solutions were synthesized by the conventional solid-state method. A perovskite-type structure was determined using the X-ray diffraction (XRD) technique. The addition of Ca²⁺ reduced the grain size (22.6, 17.9 and 13.3 μm, respectively) for all well-sintered ceramics (≈98%). Moreover, the stability temperature ranges for the tetragonal phase were promoted by displacing the ferroelectric-ferroelectric phase’s transition temperatures while T_C was maintained (86 °C). The electrical performance of the material improved as the stoichiometric composition was positioned near the morphotropic phase boundary (x = 0.15): ε_r ≈ 16,500 (T_C) at 1 kHz. For T > T_C, a thermally activated relaxation process occurred. In addition, the bulk and grain boundary processes were responsible for the conduction mechanisms. The composition x = 0.15 showed an activation energy of Ea = 1.49 eV with a maximum conductivity of σ_max = 2.48 × 10⁻² S·cm⁻¹ at 580 °C. Systematic studies at high temperature for dielectric properties were accomplished for analyzing electrical inhomogeneities associated with the grain, grain boundaries or surfaces, which are important for device design and a fundamental electrical characterization.