Self-assembly of amphiphilic small molecules in water leads to nanostructures with customizable structure-property relationships arising from their tunable chemistries. Characterization of these assemblies is generally limited to their static structures -e.g. their geometries and dimensions - but the implementation of tools that provide a deeper understanding of molecular motions has recently emerged. Here, we summarize recent reports showcasing dynamics characterization tools and their application to small molecule assemblies, and we go on to highlight supramolecular systems whose properties are substantially affected by their conformational, exchange, and water dynamics. This review illustrates the importance of considering dynamics in rational amphiphile design.