The fracture of high molecular weight poly(ethylene oxide) (PEO) chains under extensional stretching during the electrospinning of aqueous solutions was investigated by measuring solution viscosities and monitoring the change of molecular weight. The degree of macromolecular chain fractures in 1.0% polymer solutions increased with the increase in molecular weight. The strain rates for stretching and fracturing of macromolecules are critical for the degradation of polymers along with experimental elongational strain rates. (C) 2017 Wiley Periodicals, Inc.