The quinol–enedione rearrangement enables the synthesis of 2-cyclohexene-1,4-diones from readily available para-quinol substrates. Building on sporadic early reports of this transformation, we have optimized the reaction conditions and systematically investigated its substrate scope. The utility of Brønsted acid-mediated reaction conditions for a variety of quinol derivatives, including those with substituted and unsubstituted migrating termini, is highlighted. Notably, kinetic selectivity between quinol–enedione and dienone–phenol rearrangements is demonstrated. The synthetic potential of the enedione products is showcased through a range of transformations, leading to the formation of complex polycyclic structures. These findings provide a valuable framework for recognizing and applying the quinol–enedione rearrangement in synthesis, while computational studies offer valuable insights into its mechanistic underpinnings.