A method is disclosed for providing a patterned surface wherein predetermined regions of the surface are masked with a self-assembled monolayer (“SAM”) covalently bound to a brush polymer overlayer. The remainder of the substrate surface will generally be functionalized with a second self-assembled monolayer. Preferably, the method involves a microcontact printing technique, wherein a molecular moiety capable of spontaneously forming an SAM upon transfer to a surface is “stamped” onto a substrate surface, followed by growth (or covalent attachment) of a polymer on exposed functional groups within the SAM molecules. Coverage of surface regions with both an SAM and a polymer overlayer provides a number of advantages, particularly with regard to surface masking during etching and the like. The method is useful in the manufacture of microelectronic circuitry, biosensors, high-density assay plates, and the like.