Surfaces and interfaces play a critical role in determining properties and functions of nanomaterials, in many cases dominating bulk properties, owing to the large surface- and interface-area-to-volume ratio. Using Si nanomembranes, a well-controlled two-dimensional single-crystalline semiconductor, as a prototype system, we discuss how surfaces and interfaces influence electrical transport properties at the nanoscale. We show that electronic conduction in Si nanomembranes is not determined by bulk dopants but by the interplay of surface and interface electronic structures with the “bulk” band structure of the thin Si membrane. Additionally, we describe our recent experimental results on the control of highly ordered molecular structures on Si surfaces, which is of intense interest for the integration of ordered organic thin films in silicon-based electronics. This could also potentially lead to the rational design of Si nanostructures with controlled properties through regulation of the surface chemistry.