Flexible mats of titania fibers are prepared by calcination of electrospun polyvinylpyrrolidone fibers containing titanium isopropoxide precursor. Structural investigation of the calcinated nanofibers by X-ray diffraction (XRD) and electron diffraction (ED) combined with the morphologies by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show the titania fibers, with an average diameter of 180 nm, were comprised of anatase and rutile crystals. The mechanical, chemical and thermal properties of the titania fiber mats are further investigated by the techniques of Instron mechanical tester, thermogravimetric analyzer (TGA), and Fourier transform infrared spectroscopy (FT-IR). The titania fiber mat prepared in this method exhibited a significant flexibility with 461 MPa Young's modulus.