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Oxy-apatite La9.6Si6O26.4 nanofibres have been prepared by electrospinning from a sol-gel precursor solution and following calcination. The morphologies and phases of nanofibres were characterised by scanning electron microscopy, transmission electron microscopy and X-ray powder diffraction. The results showed that when the precursor nanofibres were calcined in ambient air, oxy-apatite structured La9.6Si6O26.4 was formed over the 750-900-C temperature range without any impurities. Moreover, the temperature-dependent electrical properties of La9.6Si6O26.4 nanofibres were tested by AC impedance spectra, showing an electrical conductivity of 1.5×10-2 S/cm at 600 C in air. According to the electrical tests and microstructure analysis, it was proposed that the enhanced electrical conductivity in La9.6Si6O26.4 nanofibres is mainly attributed to the oxygen-ion conduction on the surface and their nano-sized grains.