The formation of a porous polymer monolith (PPM) is influenced by the physico-chemical properties of the wall surface of its container. This influence can have a dramatic effect on the resulting monolith morphology depending on the nature and composition of the wall. Indeed, a dense polymer layer or "sheath", distinct from the bulk porous material, has been observed at the wall surface of capillaries, and thus a study was undertaken to explore the dependence of this layer on the hydrophobicity of the surface. A range of silanizing reagents were used to modify the surface of the fused silica capillary, including aminopropyl, trimethylsilyl, octadecyl and perfluorooctyl functionalities. Crosslinked butyl acrylate-based PPM was formed in the modified capillaries and extruded. SEM images of the monoliths were used to examine the sheath morphology and thickness, which are discussed with respect to surface hydrophobicity. (c) 2008 Elsevier Ltd. All rights reserved.