The interaction of hydridosilanes with oxide-free metal substrates was evaluated in order to determine their potential for surface modification analogous to alkoxysilanes with metal oxide substrates. Under mild conditions, trihydridosilanes interact with a variety of clean, hydrogenated and fresh metal and metalloid surfaces, including titanium, silicon and gold. In contrast, monohydridosilanes appear to have minimal interaction. All classes of hydridosilanes have minimal interaction with anhydrous oxide surfaces. Preliminary results suggest that surface modification with trihydridosilanes may provide a route for generating self-assembled monolayers on metal substrates. The synthesis of new trihydridosilanes is described. Contact angle, FTIR and XPS data for modified surfaces are provided. (C) Koninklijke Brill NV, Leiden, 2012