Room temperature ionic liquids (RTILs) are proposed as the alternative solvents for the acetylene separation in ethylene generated from the naphtha cracking process. The solubility behavior of acetylene in RTILs was examined using a linear solvation energy relationship based on, Kamlet-Taft solvent parameters including the hydrogen-bond acidity or donor ability (alpha), the hydrogen-bond basicity or acceptor ability (beta), and the polarity/polarizability (pi*). It is found that the solubility of acetylene linearly correlates with beta value and is almost independent of alpha or pi*. The solubility of acetylene in RTILs increases with increasing hydrogen-bond acceptor (HBA) ability of the anion, but is little affected by the nature of the cation. Quantum mechanical calculations demonstrate that the acidic proton of acetylene specifically forms hydrogen bond with a basic oxygen atom on the anion of a RTIL. On the other hand, although C-H center dot center dot center dot pi interaction is plausible, all optimized structures indicate that the acidic protons on the cation do not specifically associate with the a cloud of acetylene. Thermodynamic analysis agrees well with the proposed correlation: the higher the beta value of a RTIL is, the more negative the enthalpy of acetylene absorption in the RTIL is.