Lanthanum strontium cobalt ferrite (LSCF) nanofibers have been fabricated by the electrospinning method and used as the cathode of an intermediate-temperature solid oxide fuel cell (SOFC) with yttria-stabilized zirconia (YSZ) electrolyte. The three-dimensional nanofiber network cathode has several advantages: (i) high porosity; (ii) high percolation; (iii) continuous pathway for charge transport; (iv) good thermal stability at the operating temperature; and (v) excellent scaffold for infiltration. The fuel cell with the monolithic LSCF nanofiber cathode exhibits a power density of 0.90 W cm−2 at 1.9 A cm−2 at 750 °C. The electrochemical performance of the fuel cell has been further improved by infiltration of 20 wt% of gadolinia-doped ceria (GDC) into the LSCF nanofiber cathode. The fuel cell with the LSCF–20% GDC composite cathode shows a power density of 1.07 W cm−2 at 1.9 A cm−2 at 750 °C. The results obtained show that one-dimensional nanostructures such as nanofibers hold great promise as electrode materials for intermediate-temperature SOFCs.