A practical and tunable transition-metal-free aerobic oxidation of pyrazol-5-ones preparing either 4-hydroxypyrazoles (via C–H hydroxylation) or bispyrazoles (via dehydrogenative homocoupling) is described. The K₂CO₃/dioxane reagent system predominately promoted hydroxylation to deliver the α-hydroxylated pyrazoles. In contrast, the formation of bispyrazoles was overwhelmingly preferred with CH₃CN as the reaction medium without any additives.