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The PC-SAFT equation of state (EoS) was examined for the prediction of liquid-liquid equilibria (LLE) at high pressure on the basis of LLE data at 1 bar. New parameters set for 2-alkoxyethanol with the two-site association scheme were proposed. Mixtures of 2-alkoxyethanol with aliphatics, aromatics, alcohols, and water have been investigated. Different binary 2-methoxyethanol + alkanes systems at high pressure up to 4000 bars were also predicted using the PC-SAFT EoS. Satisfactory predictions of vapour-liquid equilibria and liquid-liquid equilibria can be achieved by using the same binary interaction parameter (kij) for a similar kind of mixtures. The results are finally compared to other association models.