Reversible solid oxide cells (RSOCs) can theoretically achieve a relatively high energy conversion efficiency. The key to its widespread application is to further enhance the current density so as to increase hydrogen production and output current. However, insufficient catalytic activity of the oxygen electrodes has become an obstacle to the application of reversible solid oxide cells. The paper successfully fabricates composite LSCF@GDC nanofibers with reversible oxygen evolution and reduction electrocatalytic activity by employing electrospinning technology. Compared with the oxygen electrodes materials synthesized by the traditional sol-gel method, the three-dimensional nanofiber structure oxygen electrodes described greatly reduces the battery polarization impedance, increases the discharge power density and electrolytic current density, and shows better reversibility and stability in long-term tests. The research confirms the advantage of electrode morphology engineering control in expanding the catalytic interface and reaction sites.