Adsorption of triethylgemane (TEG) on the Si(100) surface at 100 K has been studied using a variety of surface-sensitive spectroscopies. Thermally and electronically desorbed species were analyzed using temperature-programmed desorption (TPD) and electron-stimulated desorption (ESD) techniques. Electronically desorbed ions (H+) were analyzed using a time-of-flight technique (TOF) and time evolution studies were conducted on desorbing neutral species. Direct analysis of surface species were carried out using X-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss (HREELS) spectroscopy. Evidence is offered for (1) an electron-induced channel for direct ethylene desorption via a β-hydride elimination process; (2) an electron-stimulated transfer of ethyl ligands from a Ge to a Si site; and (3) both thermal- and electron-stimulated desorption of methyl groups. Copyright © 2006 John Wiley & Sons, Ltd.