We discuss in detail our facile method for producing supramolecular polymeric nanoparticles from the collapse of single polymer chains. A new family of poly(methyl methacrylate)-based nanoparticles confirm that our method is general and can be easily tuned toward a variety of applications. Thorough AFM characterization elucidates the conditions required to visualize single particles as well as complex assemblies of particles mediated by the evaporation of solvent. AFM studies also indicate that the intramolecular collapse resembles the cooperative folding process witnessed in biomacromolecules and that the particles possess a complex morphology that implies the internal organization of the UPy dimers used to induce the intramolecular collapse. Thermal studies support these observations in addition to confirming the applicability of this system in the fabrication of processable high-performance supramolecular materials.