Ultrafine and well dispersed CrPd nanoparticles are successfully immobilized on NH2-functionalized porous metal-organic framework MIL-101 by a facile sequential impregnation-reduction approach. By virtue of the bimetallic synergistic effect between Cr and Pd and the strong metal-support interaction between CrPd nanoparticles and MIL-101-NH2 support, the resulting Cr0.4Pd0.6/MIL-101-NH2 catalyst exhibits excellent catalytic activity for the generation of hydrogen from formic acid, affording an excellent initial turn over frequency value as high as 2009 mol H-2 mol Pd-1 h(-1) at 323 K, which is much higher than most of the reported noble metal heterogeneous catalysts for this catalytic reaction under similar conditions.