Self-assembly has been widely used for the preparation of novel nanostructured materials. To both accelerate the dynamics of this processing route and develop new nanostructures, it is critical to understand the attendant interfacial interactions that occur in solution between the different precursor components, and how such molecular level interactions affect nanostructured ordering. Extensive discussions of experimental techniques for characterizing nanoscale materials, such as small-angle X-ray or neutron scattering, high-resolution electron microscopy, and surface force microscopy can be found elsewhere. [1] This review will focus on nuclear magnetic resonance (NMR) methods, which are sensitive to local chemical environments and provide complementary information on the molecular scale, in contrast to other analytical techniques. The first section provides a brief introduction to fundamental NMR principles and their applications. It is followed by examples to illustrate how NMR can be used to derive information related to long-range ordering on the nanometer scale, the molecular conformation on a sub-nanometer scale, and their correlation to interfacial binding.