Organic monolayers on hydrogen-terminated silicon surfaces were prepared under extremely mild conditions using visible light and analyzed by a variety of surface-sensitive techniques: (angle-resolved) X-ray photoelectron spectroscopy (ARXPS), scanning tunneling microscopy (STM), high-resolution electron energy loss spectroscopy (HREELS), and attenuated total reflection infrared spectroscopy (ATR-IR). Detailed XPS and STM analysis of non-functionalized monolayers, displays detailed mechanistic and structural,information. Additionally, we present the first attachment of a disaccharide to the silicon surface, and a characterization thereof by ATR-IR and HREELS. (c) 2005 Elsevier B.V. All rights reserved.