LaCoO3 fibers were synthesized through the calcination of an electrospun polymer-metal precursor fiber. The electrochemical performance of these fibers for oxygen reduction and evolution reactions was characterized in a KOH solution. Additionally, the electrochemical properties were compared with those of a conventional PtRu/C catalyst and a LaCoO3 powder, which was synthesized using the Pechini method. The LaCoO3 fibers had a greater surface area compared with the powder, whereas the crystal structures of the fibers and powder were notably similar. The LaCoO3 fibers demonstrated better electrochemical properties compared with the LaCoO3 powder, which was attributed to the increased surface area and number of active sites in the fibers.