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[Display omitted] • DBD plasma-catalysis facilitated the RWGS reaction at low temperature. • LCNCO and LCNFO perovskite-derived bimetallic catalysts showed superior activity. • Ni-(Cu, Fe) alloys with smaller particle size promoted H 2 activation and spillover. • Higher oxygen vacancies of LCNCO and LCNFO facilitated selective formation of CO. Reverse water–gas shift (RWGS) reaction is one of the most promising and feasible CO 2 utilization strategy to generate CO, which together with renewable H 2 could be employed for Fischer-Tropsch synthesis. In this study, RWGS over La 0.9 Ce 0.1 B 0.5 B' 0.5 O 3-δ perovskite-derived bimetallic (Ni-Cu, Ni-Fe and Fe-Cu) catalysts as well as the corresponding Cu-, Ni- and Fe-based monometallic catalyst were investigated in a dielectric barrier discharge (DBD) plasma-catalysis system. The result demonstrated that the plasma-catalysis system is of great potential in promoting RWGS reaction at low temperature and atmospheric pressure. Among different catalysts, La 0.9 Ce 0.1 Ni 0.5 Cu 0.5 O 3-δ (LCNCO) and La 0.9 Ce 0.1 Ni 0.5 Fe 0.5 O 3-δ (LCNFO) exhibited higher catalytic performance in terms of CO 2 conversion (27.3–53.7% for LCNCO and 26.8–51.4% for LCNFO) and CO selectivity (59.4–94.9% for LCNCO and 58.0–91.8% for LCNFO). Their superior performance should be attributed to the formation of Ni-(Cu, Fe) alloy with smaller particle size, which facilitated the activation of H 2 and its spillover to nearby oxygen vacancies. In addition, the abundant oxygen vacancies of LCNCO and LCNFO provided sufficient active sites for CO 2 adsorption, promoting the selective dissociation of CO 2 to CO. [ABSTRACT FROM AUTHOR]