The demand for miniaturization and integration in next-generation advanced high-/pulsed-power devices has resulted in a strong desire for dielectric capacitors with high energy storage capabilities. However, practical applications of dielectric capacitors have been hindered by the challenge of poor energy-storage density (Urec) and efficiency (η) caused by large remanent polarization (Pr) and low breakdown strength (BDS). Herein, we take a method of heterovalent ion substitution engineering in combination with the multilayer capacitor (MLCC) technology and thus achieve a large maximum polarization (Pmax), zero Pr, and high BDS in the AgNbO3 (AN) system simultaneously and obtain excellent Urec and η. The substitution of Sm3+ for Ag+ in SmxAN+Mn MLCCs at x ≥ 0.01 decreases the M1-M2 phase transition temperature, and the antiferroelectric (AFE) M2 phase appears at room temperature, which is beneficial to achieving a low Pr value. Due to the low Pr value and high BDS ∼ 1300 kV·cm-1, an excellent Urec ∼9.8 J·cm-3 and PD,max ∼ 34.8 MW·cm-3 were achieved in SmxAN+Mn MLCCs at x = 0.03. The work suggests a paradigm that can enhance the energy storage capabilities of AFE MLCCs to meet the demanding requirements of advanced energy storage applications.