Two metal organic frameworks (MOFs), chromium benzenedicarboxylates MIL-101 and MIL-53, have been synthesized and used as the support of palladium catalysts. The palladium catalysts were characterized by XRD, TEM, and CO chemisorption. MIL-101 is highly hydrophilic and beneficial as support for fine Pd nanoparticles with an average size of 2.3 nm. Microporous MIL-53 is relatively hydrophobic and larger Pd particles with an average size of 4.3 nm were formed on the external surface. Pd/MIL-101 showed better phenol selective hydrogenation activity to cyclohexanone (> 98%) under mild reaction conditions because of its smaller particle size.