The control of surface chemistry and topography has great technological relevance for numerous applications of polymers in textiles, adhesives, coatings, packaging, membranes, and biomedical implants. Conventionally, chemical modification of polymer surfaces has been achieved through kinetically governed practices that allow little control over the final surface composition or morphology. These chemically generated surfaces are also prone to reconstruction. Hence the development of inexpensive, scaleable routes to impart stable and more complex chemical functionality to polymer surfaces continues to be an active area of research. Apart from surface chemistry, the topography of a polymer surface often plays a determinant role in the adhesive, optical, and wetting characteristics of the surface. Consequently methods to produce surfaces of controlled texture are also of interest. Toward these goals, new, statistical, mechanics-based theoretical approaches, coupled with increased computing power, can now facilitate the first-principles design of polymer surfaces that are chemically and structurally “tailored” for a given application. In this article, we review some of the recent, significant developments in this area.