A series of amphiphilic sulfonate-pendant platinum(II) bzimpy complexes with different lengths of alkyl chains on the alkynyl ligands has been found to show unusual absorption and emission behavior with changes to the length of the alkyl chain. The spectroscopic changes are found to be associated with the formation of self-assembled nanostructures and through the studies of their spectroscopic properties and aggregate morphology, further insights into the relationship between the molecular structures and their molecular packing are obtained.