A series of polyoxometalate-ionic liquid catalysts that combine the features of a polyoxometalate and an ionic liquid, with the introduction of acidity and miscibility, have been developed to promote the Ritter reaction. Among them, [BSmim]CuPW12 O40 [BSmim = 1-methyl-3-(4-sulfobutyl)-1 H -imidazol-3-ium] displayed the highest activity for the amidation of a variety of alcohols with nitriles, delivering the corresponding amide products in good to excellent yields. Furthermore, the reaction can be easily scaled up to a gram scale without losing efficiency. This process therefore provides an appealing way to prepare amides by a Ritter reaction using a polyoxometalate–ionic liquid-based catalyst. [ABSTRACT FROM AUTHOR]