Several chromatography systems with ionic liquids and a mixture of water with the modifier as mobile phase were characterized via the linear solvation energy relationships(LSER) model. The effects of the ionic liquids and modifier(methanol) concentrations on the retention of 10 solutes(caffeine,pyridine,aniline,phenol,methylparaben,acetopenone,m-cresol,p-cresol,o-cresol,and benzene) were discussed. The LSER model demonstrated high potential to predict retention factors with high squared correlation coefficients(r2 > 0.97). A comparison of predictable and experimental retention factors revealed that LSER can adequately reproduce the experimental retention factors of the solutes under different investigated experimental conditions. This model is a helpful tool to evaluate the retention characteristics of ionic liquid systems and to understand the interactions of solutes and ionic liquids. Several chromatography systems with ionic liquids and a mixture of water with the modifier as mobile phase were characterized via the linear solvation energy relationships (LSER) model. The effects of the ionic liquids and modifier (methanol) concentrations on the retention of 10 solutes (caffeine , LSD, pyridine, aniline, phenol, methylparaben, acetopenone, m-cresol, p-cresol, o-cresol, and benzene were discussed. The LSER model demonstrated high potential to predict retention factors with high squared correlation coefficients (r2> 0.97). A comparison of predictable and experimental retention factors revealed that LSER can adequately reproduce the experimental retention factors of the solutes under different investigated experimental conditions. This model is a helpful tool to evaluate the retention characteristics of ionic liquid systems and to understand the interactions of solutes and ionic liquids.