Multilayer ceramic capacitors (MLCCs) are essential for high-capacitance, miniaturized, and reliable electronic applications. This study examines the impact of layer stacking on the dielectric and electrical properties of MLCCs using a BaTiO₃-based dielectric with MgO, Mn₃O₄, Yb₂O₃, V₂O₅, and (BaCa)SiO₃ glass additives. MLCCs with 10 um-thick dielectric layers and varying Ni electrode layers (10, 30, 50, and 100 layers) were fabricated. The dielectric constant increases significantly up to 30 layers due to compressive stress and sintering densification but it becomes linear beyond 30 layers. Dissipation factor and ESR decrease with higher stacking due to improved sinterability, while breakdown voltage declines exponentially from defect accumulation and thermal stress. Insulation resistance decreases but stabilizes relative to capacitance. C-V results show stress-induced polarization suppression, which reduces the dielectric constant under high voltage. Optimized stacking and sintering conditions are crucial for MIL-PRF-32535 compliant MLCC designs.