Lanthanum strontium manganite (La(0.8)Sr(0.2)MnO(3), LSM) nanofibers have been synthesized by the electrospinning method. The electrospun nanofibers are intact without morphological and structural changes after annealing at 1050 °C. The LSM nanofibers are employed as the sensing electrode of an electrochemical sensor with yttria-stabilized zirconia (YSZ) electrolyte for carbon monoxide detection at high temperatures over 500 °C. The electrospun nanofibers form a porous network electrode, which provides a continuous pathway for charge transport. In addition, the nanofibers possess a higher specific surface area than conventional micron-sized powders. As a result, the nanofiber electrode exhibits a higher electromotive force and better electro-catalytic activity toward CO oxidation. Therefore, the sensor with the nanofiber electrode shows a higher sensitivity, lower limit of detection and faster response to CO than a sensor with a powder electrode.