Polyvinyl alcohol(PVA)/[La(NO3)3+Fe(NO3)3] composite nanofibers were fabricated by electrospinning, and polycrystalline LaFeO3 nanofibers were prepared by calcination of the PVA/[La(NO3)3+Fe(NO3)3] composite nanofibers at 600oC for 10h. The samples were characterized by using X-ray diffraction spectrometry(XRD), scanning electron microscopy(SEM), thermogravimetric-differential thermal analysis(TG-DTA), and Fourier transform infrared spectrometry(FTIR). The results show that PVA/[La(NO3)3+Fe(NO3)3] composite nanofibers are amorphous in structure, and pure phase LaFeO3 nanofibers are orthorhombic with space group Pn*a. The surface of as-prepared composite nanofibers is smooth, and the diameter is ca. 180nm. The diameter of LaFeO3 nanofibers is smaller than that of the relevant composite fibers. The surface of the LaFeO3 nanofibers becomes coarse with the increase of calcination temperatures. The diameter of LaFeO3 nanofibers is about 80nm, and the length is greater than 100μm. The mass of the sample remains constant when the temperature is above 500oC, and the total mass loss percentage is 90%. Possible formation mechanism of LaFeO3 nanofibers is preliminarily advanced.