An efficient and straightforward reaction protocol for the conversion of lignin model compounds was developed, based on a simple system consisting of a base, oxygen, and green solvent under mild conditions in the absence of metals. This protocol was successfully applied to the cleavage of both ‘β-O-4’ dimeric and trimeric compounds, and a controlled selective degradation was achieved depending on the bond type. The feasibility of this method to provide aromatic compounds in high yields from lignin by sequential oxidative dehomologation reaction was clearly demonstrated.