PVP/[Y(NO3)3+Al(NO3)3+Nd(NO3)3] composite fibers are prepared by electrospinning, and Nd3+∶YAG nanofibers are fabricated by calcination of the prepared composite nanofibers. X-ray diffraction (XRD) results show that the composite nanofibers are amorphous in structure, and pure phase Nd3+∶YAG nanofibers are obtained by calcination of the composite fibers at 900 ℃ for 10 h. Scanning electron microscope (SEM) analysis indicates that the diameter of the prepared Nd3+∶YAG nanofibers is about 75 nm, and the length is greater than 100 μm. Thermogravimetry and differential thermal analysis (TG-DTA) analysis reveals that the dimethylfomamide (DMF), organic compands, and nitrate salts in the composite nanofibers are decomposed and volatilized totally, the weight of the sample keeps constant when sintering temperature is above 550 ℃, and the total weight loss percentage is 84.7%. Fourier transform infrared spectrometer (FTIR) analysis manifestes that polycrystalline Nd3+∶YAG luminescant nanofibers are formed at 900 ℃. The luminescent property of Nd3+∶YAG nanofibers is investigated. The formation mechanism of the Nd3+∶YAG nanofibers is preliminarily discussed. This method can be applied to prepare other rare earths garnet-typed compound nanofibers.