In this work, nonwoven fiber mats of poly(epsilon-caprolacton) (PCL) and PCL blended with methoxy poly(ethylene glycol) (MPEG) oligomer were generated by electrospinning. The electrospinning was carried out in two different conditions depending upon the collector medium i.e. with and without water bath. It was found that the addition of MPEG increased the diameter of PCL microfibers when the electrospun mat was collected without water bath. However, the collection of microfibers into the water bath produced rice-like nanoparticles (NPs) of MPEG on the surface of PCL microfibers. The formation of hybrid mat containing hydrophobic PCL microfibers with hydrophilic MPEG hydrogel NPs is not only beneficial in future drug and gene delivery system but also useful in tissue engineering. (C) 2011 Elsevier B.V. All rights reserved.