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The physical properties (dielectric, ferroelectric, piezoelectric, etc.) of complex perovskite ferroelectrics depend on the degree of order/disorder and the scale of the ordered domains. In this study, the electrocaloric (EC) properties of three representative complex perovskite ferroelectrics, Pb(Mg 1/3 Nb 2/3)O 3 –8PbTiO 3 (PMN-8PT), 1mol% Sm-doped Pb(Mg 1/3 Nb 2/3)O 3 –8PbTiO 3 (1S-PMN-8PT) and Pb(Sc 1/2 Ta 1/2)O 3 (PST) are evaluated. Multi-layer ceramic capacitors (MLCCs) with identical structural configurations were fabricated for these three compounds, and their EC properties were characterized by direct measurement using a thermocouple. The EC temperature change Δ T of PMN-8PT, 1S-PMN-8PT and PST MLCCs under 20 V μm−1 at room temperature were found to be 1.42 K, 1.54 K, and 3.10 K, respectively. X-ray diffraction and high-resolution transmission electron microscopy data suggests that the high EC performance of PST is related to the ordering of B-site cations (Sc3+ and Ta5+) with the ordering parameter S = 0.82 and a long coherence length of ∼100 nm, such that the sample transitioned from a relaxor ferroelectric to a normal ferroelectric. These results provide pathway towards design of high performance EC materials required for solid state refrigeration and air-conditioning technologies. Multi-layer ceramic capacitors for three representative complex perovskite ferroelectrics, Pb(Mg 1/3 Nb 2/3)O 3 –8PbTiO 3 (PMN-8PT), 1mol% Sm-doped Pb(Mg 1/3 Nb 2/3)O 3 –8PbTiO 3 (1S-PMN-8PT) and Pb(Sc 1/2 Ta 1/2)O 3 (PST), were fabricated. Their EC temperature change Δ T under 20 V μm−1 at room temperature were 1.42 K, 1.54 K, and 3.10 K, respectively. The high EC performance of PST is related to the long-range ordering of B-site cations (Sc3+ and Ta5+). [Display omitted] [ABSTRACT FROM AUTHOR]