Composite SSC (Sm(0.5)Sr(0.5)CoO(3-δ))-YSZ (yttria stabilized zirconia) oxygen electrodes were prepared by an infiltration process. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) of the composite electrodes showed the formation of SSC perovskite and a well-connected network of SSC particles in the porous YSZ backbone, respectively. The electrochemical performance of the cell was investigated under both fuel cell and steam electrolysis modes using polarization curves and electrochemical impedance spectroscopy (EIS). The cell experienced a large degradation rate at 700 °C with a constant voltage of 0.7 V for over 100 h under power generation operation. The subsequent post-cell SEM micrograph revealed that agglomeration of the infiltrated SSC particles was possibly the cause for the performance deterioration. Furthermore, the long-term stability of the cell was examined at 700 °C with a constant voltage of 1.3 V under steam electrolysis mode. SEM associated with energy dispersive X-ray spectroscopy (EDS) was employed to characterize the post-test cell after the long-term electrolysis operation and it indicated that besides the agglomeration of SSC particles, the delamination of the SSC-YSZ oxygen electrode from the YSZ electrolyte, as well as segregation of cobalt-enriched particles (particularly cobalt oxides) at the interface, was probably responsible for the cell degradation under the steam electrolysis mode.