The structure and the chemical state of the metal oxide support have significant effect on the activity of noble metal nanoparticles for the catalytic oxidation of organic pollutants. In this work, we report the synthesis of porous tricobalt tetraoxide-supported palladium (Pd/Co3O4) catalysts derived from direct pyrolysis of metal-organic framework (MOF) for the complete oxidation of benzene. The porosity and nanoparticle size of the catalyst could be controlled by adjusting the calcination temperature. The X-ray photoelectron spectroscopy (XPS) analyses reveal that the surface adsorbed oxygen, which is associated with the PdO (x) species, is crucial for catalytic performance. H-2-temperature programmed reduction (H-2-TPR) results indicate that the reducibility of the catalyst has significant effect on the catalytic activity for the oxidation of benzene. In general, Pd nanoparticles supported on the porous polyhedron Co3O4 support calcined at 350 A degrees C (Co3O4-PP-350), which possess abundant porous structures and the most active surface adsorbed oxygen, exhibit the highest activity for the complete catalytic conversion of benzene compared with those supported on the porous polyhedron Co3O4 support calcined at 250 A degrees C (Co3O4-PP-250), 550 A degrees C (Co3O4-PP-550), and the Co3O4 nanoparticle support calcined at 350 A degrees C (Co3O4-NP-350).