Polyvinyl Pyrrolidone (PVP)/[La(NO3)3+Fe(NO3)3] composite nanofibers were fabricated by electrospinning. SEM micrographs indicated that the surface of the prepared composite fibers was smooth, and the diameters of the nanofibers was in the range of 1-3μm. XRD analysis revealed that the composite nanofibers were amorphous in structure. LaFeO3 nanofibers were fabricated by calcination of the PVP/[La(NO3)3+Fe(NO3)3] composite fibers. The diameters of LaFeO3 nanofibers were smaller than those of the relevant composite fibers. The surface of the LaFeO3 nanofibers became coarse with the increase of calcination temperatures. LaFeO3 hollow-centered and porous nanofibers formed by nanoparticles were acquired when firing temperature was 600-800oC. SEM images indicated that the diameters of the synthesized LaFeO3 nanofibers ranged from 500 to 800nm, and their lengths were greater than 100????m. XRD analysis revealed that LaFeO3 nanofibers were orthorhombic in structure with space group Pn*a. Possible formation mechanism for LaFeO3 nanofibers was preliminarily proposed.