To improve the hydrophilic properties of poly(epsilon-caprolactone) (PCL) nano/microfiber webs for tissue engineering scaffolds, PCL webs of various structures were fabricated by electrospinning with single or double nozzles connected to an auxiliary electrode. Surface-modified and layered PCL fiber webs were made by including water-soluble poly(ethylene oxide) (PEO) in the PCL electrospinning solution (single-nozzle method) or by electrospinning of alternating PCL and PEO solutions using two nozzles (double-nozzle method), respectively. When the PEO component within the resulting webs was removed by dissolution with distilled water, the remnant PCL webs exhibited two distinct structures. Those made by the single-nozzle method consisted of nanofibers with high surface roughness, whereas those made by the double-nozzle method consisted of stacked layers of PCL nanofibers. Both types of structured PCL web showed improved hydrophilicity characteristics compared with those of nanofiber webs generated from a pure PCL solution using a typical electrospinning process. Cell culturing and scanning electron microscopy showed that the interactions between human dermal fibroblasts and the structured PCL scaffolds were very favorable. (c) 2007 Wiley Periodicals, Inc.