TiO2 nanofibres were synthesised by means of the electrospinning technique, which were annealed at high temperatures to achieve the crystalline phase transformation. The chemical stoichiometry of electrospun TiO2 nanofibres was estimated by EDS, finding that at low annealing temperatures excess of oxygen was detected and at high temperatures excess of titanium that originates oxygen vacancies. TEM images show clearly the formation of TiO2 nanofibres that exhibit a homogeneous and continuous aspect without the presence of crystalline defects, whose surface morphology depends strongly on the annealing temperature. The crystalline phase transformation was studied by Raman spectroscopy, which revealed that annealed TiO2 nanofibres showed a crystalline phase transformation from pure anatase to, first a mix of anatase-rutile, then pure rutile as the annealing temperature increased, which was corroborated by X-ray diffraction and high-resolution TEM microscopy. The average grain size, inside the nanofibres, increased with the crystalline phase transformation from 10 to 24 nm for anatase-TiO2 and from 30 to 47 nm for rutile-TiO2, estimated by using the Scherrer-Debye equation. The band gap energy (Eg), obtained from optical absorption spectra, decreases monotonically, where a local minimum is observed at 700 °C, which is ranged in 3.75 Eg 2.42 eV, caused by the anatase → rutile crystalline phase transformation. The photoluminescence shows that radiative bands present a gradual red-shift as the annealing temperature increases due to the continuous change of Eg.