The synthesis, characterization, optical, and fluorescent properties of an amphiphilic Schiff-base bis(salicylaldiminato)zinc(II) complex are reported. Detailed (1)H nuclear magnetic resonance (NMR), diffusion-ordered spectroscopy (DOSY) NMR, optical absorption, and fluorescence spectroscopy studies indicate the existence of aggregate species in noncoordinating solvents. The degree and type of aggregation are related to the concentration and the polarity of the noncoordinating solvent. Dilute solutions are likely characterized by the presence of defined dimers, whereas larger oligomeric aggregates are conceivably formed at higher concentrations. The concentration needed to observe the formation of larger species depends upon solvent polarity. In coordinating solvents or in the presence of coordinating species, a complete deaggregation of the system occurs, because of the axial coordination to the Zn(II) ion, accompanied by considerable changes of (1)H NMR and optical absorption spectra. A dramatic enhancement of fluorescence emission is observed in dichloromethane solutions upon deaggregation with a coordinating agent. The formation of a defined 2:1 supramolecular structure is demonstrated in the case of a ditopic ligand as coordinating species. Overall, these complexes are promising systems for the development of new supramolecular architectures and supramolecular fluorescent probes.