trans-4-(Mercaptoheptoxy)stilbene (S-7-SH) was capped as a monolayer on colloidal gold clusters of diameters ranging from 1.4 to 5.2 nm. The resulting shell-core nanostructured composite showed emission from the metal and the appended arene. Differential surface area, rather than gold cluster size per se, accounted for the observed decreases in fluorescence intensity of the excited stilbene moiety upon shrinking the metal core size. Tight packing by an organic monolayer bound to the surface of the Au core was achieved most easily on large composite particles, whereas thiolatestilbene S-7-SH groups bound to the surface of the smallest metal clusters were found to be conformationally more labile.