This study aimed to use a persulfate together with transition metal ions as the reagent to effectively depolymerize lignin into monophenolic compounds under mild conditions (ambient pressure, temperature <100 °C). The Box-Behnken experimental design in combination with the response surface methodology was applied to obtain optimized reaction conditions. The results showed that this reagent could depolymerize up to 99 % of lignin dimers to mainly veratraldehyde. This reaction also successfully depolymerized industrial lignins with a high yield of phenolic oils and monophenolic compounds. Quantum chemistry calculations using the density functional theory level indicated that the persulfate free radical attacks Cβ to break the β-O-4 bond of lignin through a five-membered ring mechanism. This mechanism using persulfate free radicals has a lower activation barrier than that using hydroxyl radicals. Gel permeation chromatography and 2D-NMR spectroscopy demonstrated the effective cleavage of the β-O-4 bonds of lignin after depolymerization.