Organic-semiconductor interfaces are playing increasingly important roles in fields ranging from electronics to nanotechnology to biosensing. The continuing decrease in microelectronic device feature sizes is raising an especially great interest in understanding how to integrate molecular systems with conventional, inorganic microelectronic materials, particularly silicon. The explosion of interest in the biological sciences has provided further impetus for learning how to integrate biological molecules and systems with microelectronics to form true bioelectronic systems. Organic monolayers present an excellent opportunity for surmounting many of the practical barriers that have hindered the full integration of microelectronics technology with organic and biological systems. Of all the semiconductor materials, silicon and diamond stand out as unique. This review focuses upon the preparation and characterization of organic and biomolecular layers on semiconductor surfaces, with special emphasis on monolayers formed on silicon and diamond.