Composites were prepared using [Au(CN)(2)](-) complexes and steroidal alkaloid glycosides (SAGs) from tomato, including hydrophilic sugar and hydrophobic aglycone groups. Supramolecular sheet, tubular and unique structures were obtained, depending on the molecular structure of the SAG. Polymeric [Au(CN)(2)](n)(-) units in these supramolecular structures resulted in aurophilic interactions that produced luminescent aggregates, depending on the SAG.