Silicon is the cornerstone material of the semiconductor industry. As feature sizes on chips continue to decrease in size, the ratio of surface to bulk increases, and as a result, the role of surface defects, surface states and other subtle features play larger roles in the functioning of the device. Although silicon oxides have served the industry well as the passivation chemistry of choice, there is interest in expanding the repertoire of accessible and efficient chemical functional strategies available for use, and to fully understand the nature of these interfaces. For new applications such as molecular electronics on silicon and biochips, for example, there is a need to avoid the layer of intervening insulating oxide: A well-defined linkage of organic molecules through a silicon-carbon bond has great promise and appeal. Hydrosilylation, the insertion of an alkene or alkyne into a surface Si-H bond, is an ideal approach to producing these covalent Si-C bonds, and can be carried out in a number of ways. Light-promoted hydrosilylation is promising because it is clean and direct and can be patterned via masking; it requires no additional reagents such as catalysts or input of thermal energy and thus may have reduced surface contamination and numbers of defects. In this perspective, we start by making connections between the molecular silane literature, and the first reports of UV-mediated hydrosilylation of an alkene on a silicon surface, a reaction that was assumed to operate via a radical mechanism. We then describe the unexpected development of four new mechanisms that have no obvious parallels with the molecular silane literature, and take place as a result of the solid state electronics of the underlying silicon itself. From exciton involvement, to the influence of plasmonics, to the role of photoemission, the area of silicon surface hydrosilylation has become incredibly rich, and undoubtedly still contains new reactivity to be discovered. © 2013 American Chemical Society. ; peer reviewed: yes ; system details: This record was machine loaded using metadata from Scopus ; NRC Pub: yes