An effective catalytic system comprising a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) functionalized imidazolium salt ([Imim-TEMPO]+ X−), a carboxylic acid substituted imidazolium salt ([Imim-COOH]+ X−), and sodium nitrite (NaNO2) was developed for the aerobic oxidation of aliphatic, allylic, heterocyclic and benzylic alcohols to the respective carbonyl compounds with excellent selectivity up to >99%, even at ambient conditions. Notably, the catalyst system could preferentially oxidize a primary alcohol to the aldehyde rather than a secondary alcohol to the ketone. Moreover, the reaction rate is greatly enhanced when a proper amount of water is present. And a high turnover number (TON 5000) is achieved in the present transition metal-free aerobic catalytic system. Additionally, the functionalized imidazolium salts are successfully reused at least four times. This process thus represents a greener pathway for the aerobic oxidation of alcohols into carbonyl compounds by using the present task-specific ionic liquids in place of the toxic and volatile additive, such as hydrogen bromide, bromine, or hydrogen chloride (HBr, Br2 or HCl), which is commonly required for the transition metal-free aerobic oxidation of alcohols.