Photoluminescence of Au(I)-dodecane thiolate (Au(I)-DDT) and its thermal reduction to metallic gold have been extensively reported in the literature. However, the incorporation of this salt to a polymeric matrix to produce photoluminescent materials or gold nanocomposites by thermal reduction is a difficult task due to the insolubility of Au(I)-DDT. In this study it is shown that a silsesquioxane with pendant dodecyl chains can be a convenient host of Au(I)-DDT. The presence of dodecyl chains in both compounds and the in situ generation of the salt in the solution of the silsesquioxane precursor enabled to obtain a uniform dispersion of Au(I)-DDT in the silsesquioxane matrix. Flexible films were generated, exhibiting characteristic photoluminescent properties before thermal treatment and a uniform dispersion of gold nanoparticles after heating at 150 A degrees C for different periods of time.