The solution behavior of a series of polyethylene glycols (EO 4-35) esterified at both ends with behenic acid, H3C(CH2)(20)COOH, was evaluated in comparison with their monoesters. Understandably the solubility patterns of these esters in water are clearly governed by their hydrophilic/lipophilic balance values. The gel permeation chromatography and viscosity data strongly suggest that the disubstituted homologues are more compact than the monosubstituted counterparts both in aqueous and organic media. The ability of the diesters to aggregate in aqueous medium is established from surface tension measurements and pyrene fluorescence probe methods. The molecular area calculation based on surface tension values indicates that, at the air-water interface, the area occupied by the monoesters and diesters are comparable.