Molybdenum carbide (Mo 2 C) has emerged as a remarkable catalyst for the cleavage of the aromatic carbon− oxygen (C aryl −O) and alkyl carbon−oxygen (C alkyl −O) in lignin and lignin model compounds. However, the selectivity for the target product, that is phenol, is unsatisfactory due to the secondary alkylation reactions of the primarily produced phenol with the organic solvent used. Here, we report that a onedimensional nitrogen-doped Mo 2 C catalyst (N-Mo 2 C@C) mediated from Mo-MOF via a "pyrolysis−carbothermal reduction" process shows a remarkably high selectivity toward phenol and monophenols in the valorization of aryl ethers and lignin because of its controllable phase composition and suitable valence state. The current study provides a method to develop efficient catalysts for lignin conversion into valuable chemicals.