Polyvinyl Pyrrolidone(PVP)/[La(NO3)3+Ni(CH3COO)2] composite nanofibers were fabricated via an electrospinning technique. SEM micrographs indicated that the surface of the prepared composite fibers was smooth, and the diameters of the nanofibers were in the range of 1-3μm. XRD analysis revealed that the composite nanofibers were amorphous in structure. LaNiO3 nanofibers were fabricated by calcination of the PVP/[La(NO3)3+Ni(CH3COO)2] composite fibers. The diameters of LaNiO3 nanofibers were smaller than those of the relevant composite fibers. The surface of the LaNiO3 nanofibers became coarse with the increase of calcination temperatures. LaNiO3 porous hollow nanofibers formed by nanoparticles were acquired when firing temperature was 600-900oC. SEM images indicated that the diameters of the synthesized LaNiO3 nanofibers ranged from 500 to 800nm, and their lengths were greater than 100μm. XRD analysis revealed that LaNiO3 nanofibers were trigonal in structure with space group . Possible formation mechanism for LaNiO3 nanofibers was preliminarily proposed.