We investigate the structure and chemical nature of titania nanofibers synthesized by electrospinning techniques. Fourier transform infrared (FTIR) spectroscopy is used to identify CO2 clathrates trapped within the nanofiber structures. These molecular species are formed during pyrolysis of the guide polymer. In addition, X-ray photoelectron spectroscopy (XPS) identifies silicon within the nonwoven sheets. This led us to discover that impurities can be inadvertently incorporated during the electrospinning process from something as simple as a short piece of silicone tubing on a syringe pump. These findings should help advance the field of electrospinning by demonstrating the importance of spectroscopic characterization of materials synthesized by this technique. Copyright (C) 2006 John Wiley & Sons, Ltd.