CuNi bimetallic nanoparticles embedded in carbon matrix (CuNi@C) were synthesized and applied in the selective conversion of biomass-derived furfural to cyclopentanone. The catalysts were prepared directly from thermolysis of Cu-based metal–organic frameworks (MOFs) impregnated with nickel nitrate. Compared with traditional precipitation method, relatively high surface area (91.6m2/g) and nano-sized (about 15nm) metallic copper and nickel particles can be obtained when molar ratio of nickel to copper was 0.5. Furthermore, the porous carbon matrix can not only act as a supporter but prevent the accumulation of metal particles. By varying the molar ratio of nickel to copper, CuNi0.5@C shows best catalytic performance (99.3% conversion of furfural and 96.9% yield of cyclopentanone) at optimum conditions (130°C, 5h, 5MPa) attributed to the above mentioned properties. In addition, the CuNi0.5@C can be reused four times with good activity and stability. Hence, current work presents a new and facile method to prepare CuNi bimetallic catalysts which has a brilliant performance in catalytic conversion of furfural to cyclopentanone.