PVA/[Gd(NO3)3+Eu(NO3)3] composite nanofibres were prepared via electrospinning technique. Gd₂O₃:Eu 3+ luminescent nanofibers were synthesized by calcination of the as-prepared composite nanofibres. XRD patterns showed that the composite nanofibres were amorphous in structure,and Gd₂O₃:Eu³⁺ luminescent nanofibers were cubic in structure with space group Ia3. SEM analysis indicated that the average diameter of the composite nanofibres was about 200 nm. Gd₂O₃:Eu³⁺ luminescent nanofibers of about 50 nm in diameter were acquired when calcination temperature was 800 ℃. TG-DTA analysis revealed that the water,organic compounds and nitrate salts in the composite nanofibres were decomposed and volatilized totally,and the weight of the sample kept constant when temperature was above 600 ℃. The overall weight loss rate was 71.9%. FTIR analysis manifested that the spectrum of the composite nanofibres was almost the same as that of pure PVA,and Gd₂O₃:Eu³⁺ luminescent nanofibers were formed above 600 ℃. Fluorescence spectral analysis indicated that Gd₂O₃:Eu³⁺ luminescent nanofibers emitted bright red light of 609 nm in wavelength of Eu³⁺ ion characteristic emission under the excitation of 251 nm in wavelength of ultraviolet ray. Formation mechanism of Gd₂O₃:Eu³⁺ luminescent nanofibers was discussed. The technique can be applied to fabrication of other rare-earths composite oxides luminescent nanofibers.