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The conversion of lignin into aromatics as commodity chemicals and high-quality fuels is a highly desirable goal for biorefineries. However, the presence of robust inter-unit carbon–carbon (C–C) bonds in natural lignin seriously impedes this process. Herein, for the first time, we report the selective cleavage of C–C bonds in β-O-4 and β-1 linkages catalyzed by cheap copper and a base to yield aromatic acids and phenols in excellent yields in water at 30 °C under air without the need for additional complex ligands. Isotope-labeling experiments show that a base-mediated Cβ–H bond cleavage is the rate-determining step for Cα–Cβ bond cleavage. Density functional theory (DFT) calculations suggest that the oxidation of β-O-4 ketone to a key intermediate, i.e., a peroxide, by copper and O2 lowers the Cα–Cβ bond dissociation energy and facilitates its subsequent cleavage. In addition, the catalytic system could be successfully applied to the depolymerization of various authentic lignin feedstocks, affording excellent yields of aromatic compounds and high selectivity of a single monomer. This study offers the potential to economically produce aromatic chemicals from biomass.