The distribution behavior of n-alcohols, ketones and nitroalkanes in aqueous liquid chromatography with a column packed with polyethylene glycol (PEG) gel, TSKgel Ether-250, was compared with that in aqueous two-phase systems (ATPSs) formed from PEG and Na2SO4 or (NH4)(2)SO4. The plots of the distribution data obtained for the PEG gel system against those for the ATPS reveal that the separation selectivities exerted by the PEG gel system and the PEG-based ATPS are approximately the same. Differential scanning calorimetry studies on aqueous PEG solutions suggest that PEG polymer forms a hydration structure of which the composition is 50% (w/w) PEG or the hydration number per ethylene oxide is 2.4 and the separation selectivity of the PEG-water systems can be attributed to partition of solute compounds into the hydrated PEG polymer structure. (C) 2008 Elsevier Ltd. All rights reserved.