The influence of the microenvironment of chains on their self-organization has been studied using styrene-based linear polymers having two different pendant groups on every repeat unit. The noncovalent cross-linking of a polymer containing both carboxylic acid and alkyl (n-C10H21−) pendant groups with a multifunctional amine (PMDETA) in a nonselective solvent (DMF) resulted in thermally reversible supramolecular aggregates that were stable without interparticle cross-linking. The size of the aggregates was controlled on a sub-micrometer level by varying concentration. In the absence of the alkyl pendant group, control over the structure and properties of the aggregates was lost. These multifunctional polymers are model systems to investigate the three-dimensional organization of linear polymers by noncovalent cross-linking and the influence of chain structure on supramolecular organization.