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We have prepared the β-Ga2Oa nanofibres by electrospinning method followed by calcining in air at 900℃. The morphology and structure of the nanofibres are characterized by field emission scanning electron microscopy(FE-SEM), x-ray diffraction (XRD) and Raman technique. These nanofibres have diameters ranging from 60 to 13Onm and lengths up to several millimetres. Photoluminescence (PL) spectrum under excitation at 325nm shows that these β-Ga2Oa nanofibres have a blue emission peaking at 466nm, which may be attributed to defects such as the oxygen vacancies, gallium vacancies and gallium-oxygen vacancy pairs.