The adsorbed layers of polyoxyethylene n-alkyl ether surfactants C 12E4, C14E4, and C16E4 at the EAN surface have a headgroup layer that is thin and compact (only ∼ 30 vol % EAN). The headgroups do not adopt a preferred orientation and are disordered within the ethylene oxide layer. Alkyl tails contain a significant number of gauche defects indicating a high degree of conformational disorder. The thickness of the tail layer increases with increasing alkyl chain length, while the headgroup layer shows little change. Lowering the C12E 4 concentration from 1 to 0.1 wt % decreases the adsorbed amount, and the headgroup layer becomes thinner and less solvated, whereas C 14E4 and Ci6E4 adsorbed layers are unaffected by dilution over the same concentration range. The C16E4 layer thickness increases and area per molecule decreases on warming to 60 °C, but the adsorbed layer structures of C12E4 and C 14E4 are unchanged. Both effects are attributed to surfactant solubility.