We have studied the self-assembly of thiol monolayers on high-area nanostructured gold surfaces. These surfaces are highly irregular with a fractal dimension close to 2.5. Auger electron spectroscopy and voltammetric data indicate that thiol self-assembly with a maximum surface coverage approximate to (1)/(3) takes place, the same result as that found for smooth gold surfaces. Therefore, neither curvature effects, which would promote higher coverage, nor excluded volume effects, which would result in lower coverage, are present in these irregular surfaces. The high surface area of the bare electrodes exhibits a rapid surface decay in different liquid media that is hindered by alkanethiolate chemisorption. The presence of thiolate SAMs reduces markedly the mass transport surface diffusion of gold adatoms, hindering surface area decay and freezing the system in a metastable state for days. This effect cannot be explained by considering only hydrocarbon-hydrocarbon chain interactions, because it is also observed for ordered arrays of adsorbed S atoms. Therefore, interactions between ordered chemisorbed species at high coverage seem to be responsible for the observed behavior. The thiol-covered high-area metallic substrates can be used to efficiently anchor a large number of molecules, biomolecules, or nanostructures, improving the performance of SAM-based optical and electrochemical devices.