A strategy for the highly efficient synthesis of 3(2H)-furanones by hydration of diyne alcohols catalyzed by base-functionalized ionic liquids under atmospheric-pressure CO2 that was developed through computer-assisted design is reported. The best range of basic ionic liquids as catalysts was predited at first, and [HDBU] [BenIm] exhibited the highest catalytic activity. Through a combination of. NMR spectroscopic investigations and quantum-chemical calculations, the results indicated the importance of the basicity of the anion and the species of cation in the ionic liquid.