Tailoring the surface properties of semiconductor materials through organic modification is one means of providing new functionality to the semiconductor surface, incorporating properties such as passivation, lubrication, optical response, molecular recognition, or biocompatibility. Chemical modification also has tremendous utility for the controlled synthesis of organic/semiconductor interfaces for numerous electronic and optical applications, including the coupling of organic-based devices to silicon-based microchip technology. In this presentation, I will discuss different organic attachment strategies used to functionalize semiconductor surfaces in a dry processing environment. Unsaturated molecules, such as alkenes or dienes, can be attached by cycloaddition reaction across the Si-Si dimer at the Si(100)-2x1 surface; the reaction occurs at the surfaces of Ge and diamond, as well. Amine groups provide another reactive functionality for surface attachment. The relative reactivities of cycloaddition, N-H bond dissociation, and nitrogen lone pair interactions at the Si(100)-2x1 surface will be described using a series of pyrrole compounds. The use of protecting groups to manipulate the surface reaction pathway will be demonstrated. The potential for these different classes of attachment reactions to impact future applications will also be discussed.