Value-added utilization of lignin waste streams is vital to fully sustainable and economically viable biorefineries. However, deriving substantial value from its main constituents is seriously hindered by the constant requirement for expensive coenzymes. Herein, we devised a coenzyme-free biocatalyst that could transform lignin-derived aromatics into various attractive pharmaceutical and polymer building blocks. At the center of our strategy is the integrated use of new mining phenolic acid decarboxylase and aromatic dioxygenase with extremely high catalytic efficiency, which realizes the value-added utilization of lignin in a coenzyme-independent manner. Notably, a new temperature/pH-directed strategy was proposed to eliminate the highly redundant activities of endogenous alcohol dehydrogenases. The major components of lignin were simultaneously converted to vanillin and 4-vinylphenol. Since the versatile biocatalyst could efficiently convert many other renewable lignin-related aromatics to valuable chemicals, this green route paves the way for enhancing the entire efficiency of biorefineries.