Directional regulation for the reaction pathways of lignin-related compounds represents a meaningful process for obtaining value-added chemicals. Herein, a series of Pd-based, Nibased, and Pd-Ni catalysts were used to investigate the conversion pathways of the lignin-derived aryl ethers. It was found that Pdbased catalysts easily induced partial hydrogenation-reductive hydrolysis of diphenyl ether (DPE), while DPE underwent direct hydrogenolysis and partial hydrolysis over Ni-based catalysts. DPE was converted to high-yield cyclohexanol by direct catalytic hydrolysis/hydrogenolysis over a bimetallic Pd-Ni catalyst. 3% Pd-1%Ni/AC exhibited superior performance that outperformed the monometallic catalysts (1%Ni/AC and 3%Pd/AC) and mixed 1%Ni/AC and 3%Pd/AC under the equal conditions. The characterization results revealed that electron transfer from Pd to Ni, led to a strong interaction between Pd and Ni. The electronic deficient Pd possessed optimized H 2 activation ability, and the inserted Ni was conducive to the cleavage of DPE. The deuterium experiment and reaction kinetic study demonstrated that DPE was cleaved to 75.7% cyclohexanol via catalytic hydrolysis/ hydrogenolysis over 3%Pd-1%Ni/AC. Besides, other lignin-related compounds could also be converted into high-value-added chemicals over 3%Pd-1%Ni/AC by cleaving the C−O bond.