Supramolecular polymer complexes with small molecules are self-assembled through non-covalent interactions and have been proposed for a wide variety of applications in materials science and nanoscience. Our research group has recently shown the possibility of forming highly ordered nanofibers of supramolecular complexes in their thermodynamically stable state using the electrospinning technique. The ultrafast solvent evaporation rate of electrospinning made possible the in-depth characterization of complexes that had never been prepared in their pure state before because of kinetic issues associated with their formation by conventional approaches. The improved understanding of the formation mechanism allowed us to extend the concept to other techniques featuring a fast solvent evaporation rate, such as electrospray and spin-coating. In this article, we review our most significant contributions in this research field.