Self-supported translucent films constituted of poly(n-octylsilsesquioxane) or poly(n-dodecylsilsesquioxane) were obtained from the hydrolysis and condensation of n-octyltriethoxysilane (OTES) or n-dodecyltriethoxysi lane (DTES), respectively. Dense films were obtained in the absence of organic solvents, with dibutyltin diacetate as catalyst. These films exhibited good optical transparency and thermal stability. The incorporation of oligomeric dimethylsiloxane units (D-Me,D-Me) in these materials, derived from silanol-terminated poly(dimethylsiloxane) (PDMS) or 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane (TMDES), was carried out during the hydrolysis and condensation of OTES and DTES and was confirmed by solid-state Si-29 NMR. Poly(n-octylsilsesquioxane) showed a glass-transition temperature at -65 degrees C, due to the increase in the free volume, promoted by the bulky n-octyl groups. The differential scanning calorimetric (DSC) curves of the polymer derived from DTES were characterized by first-order transitions at temperatures ranging from -15.8 to -0.7 degrees C. Further studies of these networks by low-temperature XRD evidenced narrowing of the diffraction halos suggesting a partial order-disorder transition for these materials at lower temperatures. Good thermal stability up to 350 degrees C and the solvent-free production process make these polymers potential candidates for the development of self-supported hydrophobic protective coatings. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1220-1229, 2010