Cyclohexanone is a simple and widely available raw material that can be obtained from lignin biomass, highlighting its renewable and sustainable features. Cyclohexanone, as an important synthon in organic chemistry, has been demonstrated to be viable for constructing functionalized arenes and benzoheteroarenes, with recent extensive development on transition metal-free oxidative dehydrogenative aromatization. This review focuses on recent research progress on the transition metal-free derivation of cyclohexanones via oxidative dehydrogenative aromatization.