The catalytic depolymerization process for lignin to produce value added chemicals is often challenged by the limited mass transfer over heterogeneous catalysts, the complex aromatic biopolymer structures, and the high recalcitrance of C-C bonds. Herein, a series of hierarchical MFI nanosheets (MFI-ns) supported metal oxide catalysts have been designed and used for the selectively oxidative cleavage of organosolv lignin. As expected, 81.6 % conversion of lignin can be achieved over 15Ce-5Cu/MFI-ns with 294.0 mg g(-1) yield of volatile products, including 180.9 mg g(-1) of diethyl maleate. Quantum chemistry calculation coupled with static adsorption measurements shows that the superior catalytic activities of these catalysts are ascribed to the favorable mass transport of lignin to the active sites by the unique layer structure, and the hierarchical pore sizes distribution, as well as the electronic effect between Cu and Ce components. In addition, the catalytic mechanism for the cleavage of C-C bonds in beta-O-4 model probes has been studied via the controlled oxidative degree of model compounds and the isotope-labeling experiments. Therefore, this work provides a new insight into the efficient utilization of lignin via the rational design of catalysts.