Although it is known that metallic silver can be produced by the thermal decomposition of silver n-dodecanethiolate (Ag-DDT), the use of this reaction to synthesize silver-modified coatings is difficult due to the insolubility of Ag-DDT in most solvents and coating precursors. We report that lamellar Ag-DDT crystals can be uniformly dispersed in an organic-inorganic hybrid coating based on a bridged silsesquioxane containing pendant dodecyl chains. Heating the dispersion for 4 h at 423 K (above the melting point of the Ag-DDT crystals) produced the transformation of the lamellar phase into a metastable crystalline phase together with a spiral-like microstructuration of the whole material. When the heating was continued for 24 h, the metastable crystalline phase led to metallic silver microstructures uniformly dispersed in the silsesquioxane matrix. (C) 2011 Elsevier B.V. All rights reserved.