Potential applications of ionic liquids (ILs) for the green separation process of acetylene in ethylene and for the storage of acetylene were investigated. To deal with this proposal, the solubilities of the unsaturated hydrocarbons in various ionic liquids were evaluated. The solubility of ethylene shows a solubility parameter-dependent behavior as indicated by the proportional relationship between the natural log value of Henry's law constant and the inverse molar volume of ILs. This correlation suggests the most important role of voids formation within IL to accommodate the solutes and the applicability of regular solution theory to model the solubility behavior. Whereas, in addition to the free-volume contribution of ILs, the solubility of acetylene is largely controlled by a specific solute-solvent interaction as a result from the association of the acidic hydrogen character in acetylene and the relative basicity of the anion. Those two different solubility behaviors result in a high absorption selectivity of acetylene over ethylene in the basic ILs. H-1 NMR experiment clearly demonstrated the presence of a substantial interaction between the acetylene and the anion of IL Interestingly, this solute-solvent interaction is reversible as indicated by the absorption-desorption test of acetylene in [BMIM][Me2PO4]. (C) 2010 Elsevier B.V. All rights reserved.