A series of novel bi-SO3H-functionalized ionic liquids were synthesized and acted as catalysts for the synthesis of β-acetamido ketones. Compared with traditional single-SO3H- functionalized ionic liquids, less amount of catalysts, higher yields and shorter reaction time are the key features of this methodology. Hammett function values and the minimum-energy geometries of bi-SO3H-functionalized ILs were calculated and the results revealed that ...