Multilayer ceramic capacitors (MLCCs) for electric vehicles require their room temperature capacitance to change ≤ ±15% at −55°C to 200°C. The dielectric constant (ε) of BaTiO3, a dielectric material widely used in MLCCs, drops at >125°C making its application to electric vehicles difficult. Here, we propose KCa2Nb3O10 (KCNO)-layered perovskite as a strong candidate for electric vehicle MLCCs as its ε does not change abruptly with temperature. The effect of sintering temperature on the temperature coefficient of capacitance (TCC) of KCNO is studied. The KCNO powder calcined at 900–1200°C is sintered at 1200°C–1300°C. Microstructure and temperature-dependent ε are determined by the sintering temperature, while the sintered density is related to the difference between the calcining and sintering temperatures. Only the room temperature ε of the samples sintered at 1300°C (except the one calcined at 900°C) varies ≤ ±15% at 25°C–200°C (ε ~250 at room temperature). The sample calcined at 1100°C and sintered at 1300°C has highly elongated grains and the highest activation energy. These factors are responsible for the TCC of the 1300°C sintered KCNO being ≤ ±15% at 25–200°C.