A methoxy poly(ethylene glycol) (MPEG) oligomer with a viscous nylon-6 supporting solution was fabricated and polymerized simultaneously to form a nanofiber network structure via electrospinning. This network consisted of thin MPEG nanofibers and thick nylon-6 nanofibers, which were arranged in a spider-web like structure. These two different nanofibers were separated from the electrospun mat by extraction of MPEG using water. This result showed that the hybrid nanocomposite mat consisted of two different interconnecting polymeric nanofibers. We propose that this interconnection is due to the formation of hydrogen bonds between MPEG and nylon-6 molecules. This spider-web structure formed by electrospinning was responsible for increasing the mechanical strength and the wetability of nylon-6 mat in the presence of small amounts of MPEG. (C) 2010 Elsevier B.V. All rights reserved.