AbstractA new linear solvation energy relationship (LSER) equation, where the solute internal energy term has been incorporated into the traditional LSER equation, is used for the analysis of solvation in ionic liquids. Modeling results obtained using the new LSER equation indicate that all solute parameters (dispersion, polarity, hydrogen bonding, cavity formation, and solute internal energy) have approximately equal importance in the solvation of organic solutes in ionic liquids. The magnitude of dispersion interaction is stronger in ionic liquids than in aqueous solution, whereas hydrogen‐bonding interactions are stronger in water than in ionic liquids. This indicates that the solubility of polar compounds that contain bulky and aromatic groups can be enhanced in ionic liquids due to higher dispersion interactions in ionic liquids than in aqueous solution. On the other hand, the LSER equation without the solute internal energy term does not yield the meaningful solute–solvent interaction terms, indicating that the inclusion of a solute internal energy term is necessary to properly describe the solvation of organic solutes in liquid solvents. Copyright © 2004 Society of Chemical Industry