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We report on bimetallic FeRh clusters with a narrow size-distribution grown on graphene on Ir(111) as a carbon-supported model catalyst to promote low-temperature catalytic CO oxidation. By combining scanning tunneling microscopy with catalytic performance measurements, we reveal that Fe-Rh interfaces are active sites for oxygen activation and CO oxidation, especially at low temperatures. Rh core Fe shell clusters not only provide the active sites for the reaction, but also thermally stabilize surface Fe atoms towards coarsening compared with pure Fe clusters. Alternate isotope-labelled CO/O-2 pulse experiments show opposite trends on preferential oxidation (PROX) performance because of surface hydroxyl species formation and competitive adsorption between CO and O-2. The present results introduce a general strategy to stabilize metallic clusters and to reveal the reaction mechanisms on bimetallic structures for low-temperature catalytic CO oxidation as well as preferential oxidation.