In the present contribution, successful preparation of ultrafine fibers of poly(ethylene glycol)-polydimethylsiloxane-poly(ethylene glycol) (PEG-PDMS-PEG) triblock copolymer in its blends with poly(ethylene oxide) (PEO) via electrospinning process was reported for the first time. Chloroform was used as the solvent, the compositional weight ratios between the copolymer and PEO were 80/20, 70/30, and 60/40 and the total concentration of the solutions was either 4 or 6% w/v. While pure PEG-PDMS-PEG solutions in chloroform were not electrospinnable into fibers, the solutions that contained PEO were. The improvement in the electrospinnability of the PEG-PDMS-PEG solutions in the presence of PEO was thought to be due to the increase in the viscosity of the resulting solutions. The average diameter of the fibers obtained ranged between 2.3 and 2.8 mu m. Fourier-transformed infrared spectroscopy measurements confirmed the existence of the copolymer within the as-spun blend fibers. (c) 2006 Elsevier B.V. All rights reserved.