Size-controlled gold nanoparticles/surfactant stable systems were prepared by the combined action of the solvated metal atom dispersion (SMAD) technique and confinement in anhydrous sodium bis(2-ethylhexyl)sulfosuccinate (AOT) micellar solution. From liquid samples, by evaporation of the organic solvent, solid gold nanoparticle-surfactant liquid crystals composites were obtained. Sample characterization was performed by X-ray diffraction (SAXS and WAXS), XPS spectroscopy and UV-vis-NIR spectroscopy. All experimental data consistently revealed the coexistence of two gold nanoparticle size populations: bigger nanoparticles (size 20-50 angstrom) and smaller ones (size of few angstrom). The two differently-sized gold nanoparticles can be separated by resuspending the gold/surfactant nanocomposite in n-heptane. This operation causes the slow selective precipitation of the bigger nanoparticles softly coated by surfactant leaving, in the surnatant, only the smaller Au nanoparticles. The latter were found to be entrapped in the core of AOT reversed micelles and stabilised by the surfactant adsorption on their surface. Such nanoparticles, as shown by SAXS data, slowly rearrange to a narrower size distribution giving a surnatant containing stable and finely size-controlled gold nanoparticles. (c) 2005 Elsevier B.V. All rights reserved.