Catalytic hydrogen production from formic acid has been reported to be an efficient method for hydrogen generation and storage. In this study, the mullite-type SmMn 2 O 5 is first synthesized by coprecipitation, and then the extra-fine bimetallic PdCr NPs with dimensions of 2.05 nm are successfully anchored on the surface of amine-functionalized SmMn 2 O 5 by a one-step wet chemical method. The obtained PdCr/OPDA-SmMn 2 O 5 shows good catalytic activity and the turnover frequency (TOF) value of 1028 h −1 at 323 K, which is in line with most reports. Notably, the catalyst remains stable and active under five cycle performance tests with no significant agglomeration after the reaction. The remarkable catalytic performance is attributed to the formation of small and highly dispersed PdCr NPs after the introduction of amino groups. In addition, the synergistic effect between the bimetal and the support effectively accelerates the catalytic efficiency of the bimetal system. This study provides an idea for the development of amine-modified bimetallic-loaded catalysts.