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Lignin, as a structurally complex biomaterial, offers a valuable resource for the production of aromatic chemicals; however, its selective conversion into desired products remains a challenging task. In this study, we prepared three types of Pd-based nano-catalysts and explored their application in the depolymerization of alkali lignin, under both H₂-free (hydrogen transfer) conditions and H₂ atmosphere conditions. The materials were well characterized with TEM, XRD, and XPS and others, and the electronic interactions among Pd, Ni, and P were analyzed. The results of lignin depolymerization experiments revealed that the ternary Pd-Ni-P catalyst exhibited remarkable performance and guaiacols could be produced under H₂ atmosphere conditions in 14.2 wt.% yield with a selectivity of 89%. In contrast, Pd-Ni and Pd-P catalysts resulted in a dispersed product distribution. Considering the incorporation of P and the Pd-Ni synergistic effect in the Pd-Ni-P catalyst, a possible water-involved transformation route of lignin depolymerization was proposed. This work indicates that metal phosphides could be promising catalysts for the conversion of lignin and lignin-derived feedstocks into value-added chemicals.