Liquid-liquid equilibrium data were measured at 293.15 K for the quaternary system sulfolane + 2-methoxyethanol + octane + toluene. The Othmer and Tobias method satisfactorily correlated tie-line data. The nonrandom two-liquid (NRTL) equation was used to correlate the experimental data and to predict the phase composition of the systems studied here. The agreement between the correlated and experimental results was good.