Electrochemical catalysis emerges as a promising method for lignin depolymerization due to its environmental friendliness and mild reaction condition. Metal oxyhydroxides have displayed appealing electrochemical activity for the oxidation for various biomass substrates. In this study, we prepared different metal (Ni, Co, Mn, Fe, and Cu) oxyhydroxides on nickel foam electrodes through electrodeposition. Their electrochemical properties were characterized and the reactivity towards lignin oxidative cleavage was investigated using lignin model compounds. NiOOH exhibited significantly higher activity for oxidative cleavage of the β-O-4 linkage compared to other metal oxyhydroxides, resulting in a 93% yield of aromatic monomers with 99% selectivity towards benzoic acids. Furthermore, the reconstruction process of the active site NiOOH was revealed by in-situ testing, and the reaction mechanism was explored. The non-phenolic structure underwent C_β–C_γ/C_β–O or C_α–C_β cleavage, predominantly producing benzoic acids, while the phenolic structure was rapidly oxidized into dicarboxylic acids over NiOOH.