A novel series of pyrrolidine-based chiral pyridinium ionic liquids (ILs) have been developed by using commercially available ( S)-(2-aminomethyl)-1- N-Boc-pyrrolidine. These chiral ILs have been found to be recyclable and efficient organocatalysts for the asymmetric catalytic Michael addition reactions of ketones to nitroolefins with high yields, high enantioselectivies, and diastereoselectivies.