Erbium(III) doped TiO2 nanofibers (Er2Ti2O7) have been synthesized by electrospinning mixtures of polymers, metal-containing materials, and erbium acetate. These electrospun nanofibers were subsequently annealed at temperatures of 550, 750, 950, and 1150 oC to remove the organics and leave behind the metal oxides. The crystal structure and optical properties of the nanofiber pyrochlores were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transformation IR (FTIR) spectroscopy. Different crystal structures were formed by controlling the annealing conditions. XRD data are compared with near-IR spectra to better understand the effects of annealing temperature on the Er (III) thermally-excited selective optical emission process.