Microemulsions are increasingly employed within industrial processes in the pharmaceutical, 1,2 food, 3 cosmetics 4 and petroleum industries, as well as in fundamental technologies like chemical separations. Molecular level details of microemulsion structure is a growing area of interest, as more evidence is demonstrating that intermolecular interactions between the assembled amphiphiles tune the size, shape and inter-micelle interactions within the solution. A number of features influence intermolecular interactions, including the molecular conformation of amphiphiles (through modulation of the dipole moment and molecular packing). The conformational potential energy landscape (PEL) for amphiphiles has a topology that is dictated not only by intramolecular degrees of freedom and interactions (e.g., internal hydrogen bonds) but also by how different conformations are influenced by direct solvent-solute interactions. It is possible to control morphological characteristics of the self-assembled aggregates by exploiting solvent or solution properties (e.g., through polarity), yet the direct correlation of local solvation upon conformation ensembles of individual amphiphiles (and the impact this has upon aggregation) has not been well-established. In part, this is because sampling the conformational landscape of amphiphile monomers under different solution conditions is a significant experimental challenge.