The increased interest in the utilization of lignin in biobased applications is evident from the rise in lignin valorization studies. The present study explores the responsiveness of lignin toward oxidative valorization using acetic acid and hydrogen peroxide. The pristine lignins and their oxidized equivalents were analyzed comprehensively using NMR and SEC. The study revealed ring opening of phenolic rings yielding muconic acid- and ester-end groups and side-chain oxidations of the benzylic hydroxyls. Syringyl units were more responsive to these reactions than guaiacyl units. The high selectivity of the reaction yielded oligomeric oxidation products with a narrower dispersity than pristine lignins. Mild alkaline hydrolysis of methyl esters enhanced the carboxylic acid content of oxidized lignin, presenting the potential to adjust the carboxylic acid content of lignin. While oxidation reactions in lignin valorization are well documented, this study showed the feasibility of employing optimized oxidation conditions to engineer tailored lignin-based material precursors.