Metallosalphen complexes with peripheral glucose and galactose substituents were synthesized and characterized. Their self-assembled supramolecular structures were then studied with transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). It was found that all of the complexes displayed aggregation in the solid-state. Zinc-salphen complexes showed a remarkably homogeneous helical nanofibrillar morphology, whereas the other metal complexes only displayed micron-sized clusters.