In this work, we describe the synthesis of nanostructured polymeric materials of controlled tubular geometries using oxygen plasma and polysiloxane-grafting onto electrospun fiber sacrificial templates. The fibers were characterized using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) to determine the extent of grafting, graft chemistry and the influence of plasma treatment. Scanning electron microscopy (SEM) was used to determine the morphology and size of the electrospun fibers and nanotubes. The average diameter of the electrospun fibers employed ranged between 300 nm and 1500 nm. The micrographs revealed differences that are dependent on the type of grafting chemistry as well as plasma treatment times. The template synthesis of polysiloxane nanotubes using polyester track-etched membranes also shows that the technique is applicable to different substrates. (C) 2007 Elsevier B.V. All rights reserved.