Nanometric inorganic pigments are widely used as fillers for hybrid composite materials. However, these nanometric powders are hydrophilic in nature and their surface must be functionalized before use. In this work, titanium dioxide (TiO2) nanoparticles were coated using silane coupling agents with alkyl functionality. A supercritical carbon dioxide (scCO(2)) method was used for surface silanization. Five alkylalkoxysilanes with different alkyl chain length and structure were studied: methyltrimethoxy, isobutyltriethoxy, octyltriethoxy, octyldimethylmethoxy and octadecyltrimethoxysilane. The microstructure and thermal stability of deposited monolayers were characterized using thermogravimetric analysis, ATR-IR spectroscopy, transmission electron microscopy, wettability characterization and low-temperature N-2 adsorption/desorption analysis. The use of scCO(2) as a solvent provided an effective approach to functionalize individual inorganic nanoparticles due to the enhanced diffusivity of the solution molecules in the aggregates interparticle voids. The trifunctional silanes employed here yielded surfaces with better thermal stabilities and greater hydrophobicities than the used monofunctional silane. (C) 2009 Elsevier Inc. All rights reserved.