Polyvinylpyrrolidone (PVP)/La0.6Sr0.4Co0.4 Fe0.6O3(LSCF) composite nanofibers were fabricated via electrospinning technique and sol-gel process. Single crystal LSCF nanofibers were prepared after the composite fibers calcined at different temperatures. And the morphology, phases, structure, heat treatment and electrical property of the nanofibers were characterized. The results show that moisture and organic matter in PVP/LSCF composite fiber had volatilized and decomposed completely while the temperature was 560°C. LSCF nanofibers can be prepared from PVP/LSCF composite fibers with rhombohedral structure by the calcined processing. The LSCF nanofiers have a uniform diameter of 130-240 nm after calcined at 800°C. The single cell with LSCF nanofiers as cathode had good electrical property. The maximum power density of the single cell with nano LSCF fiber as cathode at 750°C were 1.18 W/cm2. The electrical property of the fibers is better than that of the LSCF powders prepared by traditional sol-gel method.