A single- and a double-tailed cationic surfactant with the triallylammonium headgroup formed reverse micelles (RMs) in heptane/chloroform containing a small amount of water. The reverse micelles were cross-linked at the interface upon UV irradiation in the presence of a water-soluble dithiol cross-linker and a photoinitiator. The resulting interfacially cross-linked reverse micelles (ICRMs) of the single-tailed surfactant aggregated in a solvent-dependent fashion, whereas those of the double-tailed were identical in size as the corresponding RMs. The ICRMs could extract anionic metal salts, such as AuCl4− and PtCl62−, from water into the organic phase. Au and Pt metal nanoparticles were produced upon reduction of metal salts. The covalent nature of the ICRMs made the template synthesis highly predictable, with the size of the metal particles controlled by the amount of the metal salt and the method of reduction. Nanoalloys were obtained by combining two metal precursors in the same reaction. Reduction of the ICRM-entrapped aurate also occurred without any external reducing agents, and the gold nanoparticles differed dramatically from those obtained through sodium borohydride reduction. The same template allowed the preparation of luminescent Au4, Au8, and Au13−Au23 clusters, as well as gold nanoparticles several nanometers in size, simply by using different amounts of gold precursor and reducing conditions.