We outline a method to fabricate gradient combinatorial libraries that explore architectural parameters of surface-grafted block copolymers (BCs). In addition, we demonstrate the utility of such libraries for the rapid, thorough assessment of the response of grafted BCs to solvent exposure. Our fabrication route uses surface-initiated controlled radical polymerization to produce a tethered polymer block with uniform length (in this case, poly(n-butyl methacrylate), PBMA), followed by a graded synthesis that adds a second block that varies in its length over the library (here, poly(2-(N,N'-dimethylamino)ethyl methacrylate), PDMAEMA). Our demonstration study maps the response of PBMA and PDMAEMA blocks to hexane and water, and defines regimes of behavior to this respect. Moreover, our study illuminates a narrow BC composition window that exhibits the strongest possible response to water and hexane treatment. (c) 2005 Elsevier B.V. All rights reserved.