Novel LaFeO3 ribbon-like porous nanofibers have been fabricated by electrospinning utilizing sol-gel precursors, followed by heat treatment at 600 degrees C for 2 h. The crystal structure, surface morphology, and microstructure were investigated by thermogravimetry-differential thermal analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, respectively. The photocatalytic activity was investigated for the photodegradation of methylene blue aqueous solution. The result shows that the ribbon-like porous nanofibers exhibit excellent photocatalytic activity compared with ultrafine LaFeO3 nanofibers and LaFeO3 powders.