Solutions of surfactants of differing concentrations in polyoxypropylene glycol have been investigated by electron microscopy, NMR and surface tension methods. It is shown that the introduction of surfactants leads to a morphological transition in surface layers of the oligoether, and this is related to a change in their energetic and entropic states. In the interval of surfactant concentration from 0 to 0·3% it was found that a 0·03% concentration corresponds to a reorientation of sufractant molecules in surface layers, thus ensuring their stability. The formation of micelles in these solutions at a surfactant concentration of 0·15% is preceded by an extremal type of change in thermodynamic functions of surface layers of the surfactants.