An experimental study of the derivatization of Si(100) surfaces with 1‐octyne has been carried out via x‐ray photoelectron spectroscopy at different take‐off angles, and infrared absorption spectroscopy in attenuated total reflection mode and atomic force microscopy have been used to characterize the pristine surface. Our study has shown that it is possible to prepare nearly flat, terraced, homogeneously hydrogen‐terminated Si(100) surfaces via exposure to H2 at high temperature (1100 °C) and that these surfaces may be functionalized with hydrocarbon moieties by simple immersion in the unsaturated hydrocarbon at ∼200 °C. Copyright © 2004 John Wiley & Sons, Ltd.