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The development of high-performance electrocaloric (EC) materials is crucial for solid-state refrigeration applied in micro-electromechanical systems. Herein, a large room-temperature EC response is realized in (1 – x)­(K0.49Na0.49Li0.02)­(Nb0.8Ta0.2)­O3–xCaZrO3 (KNLNT–xCZ) benefiting from a relaxor enhancement effect and multilayer ceramic construct. The relaxor enhancement effect is because the long-range order is broken by adding CaZrO3, which is in favor of enhancing the temperature change (ΔT) and broadening the temperature span (T span) at room temperature. A ΔT of 0.48 K in the KNLNT–12CZ ceramic is ∼5 times higher than that in the KNLNT–8CZ ceramic at 30 °C. KNLNT–12CZ also exhibits good temperature stability, and the T span is up to 65 K. In addition, the multilayer ceramic construct improves the breakdown electric field (E b) through diminishing defects, leading to a booming ΔT of 3.2 K at 30 °C under 250 kV cm–1 via a direct measurement. The work proposes an avenue for developing high-performance EC materials with a large EC response and broad T span in solid-state refrigeration.

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