In recent years, ionic liquids have been extensively used in many organic synthesis reactions as potential green alternative solvents and catalysts. The asymmetric aldol reaction is one of the most efficient processes for the synthesis of optically active â-hydroxy carbonyl compounds which are important intermediates. The asymmetric aldol reaction have been extensively used to prepare pharmaceutical, pesticide, and flavor chemicals, have high yields and stereoselectivity and have good application foreground. Coordinated ionic liquids are new compounds on the basis of traditional ionic liquids, which have the same general nature as traditional ionic liquids, such as negligible vapor pressure, nonflammability, high thermal stability, electric chemistry window way big and wide liquid temperature range. Coordinated ionic liquids have a number of advantages over traditional ionic liquids including simple synthesize methods, short respond time, cheap raw material and atom-economy. In this study, four kinds of coordinated ionic liquids were synthesized using caprolactam and salts, which were confirmed by IR and NMR. In coordinated ionic liquids, direct asymmetric aldol addition of benzaldehyde and 2-butaneone was investigated using L-proline as a chiral catalyst. The influences of various reaction parameters such as reaction time, respond temperature, cycle times, different coordinated ionic liquids and different molar ratios were discussed. The product was easily isolated and the coordinated ionic liquid could be reused at least 4 times with almost the same efficiency. Using this method, the asymmetric aldol reaction was not only simplified but also a potential green alternative over traditional method.