Abstract The single component fuel cell (SCFC) is a novel physical-electrochemical device for energy conversion which is recently discovered. The functional composite materials of Li0.15Ni0.25Cu0.3Zn0.3O2−δ (LNCZO) and Ce0.8Sm0.2O1.9 (SDC)-carbonate are proved as unique materials in SCFC (or one-layer fuel cell). In this work, the microstructure and morphology of two composite materials of LNCZO-SDC-Na2CO3 (LNCZO-NSDC) and LNCZO-SDC-(Li/Na)2CO3 (LNCZO-LNSDC) are investigated by SEM-EDX and HR-TEM. Their catalytic activities for both hydrogen oxidation and oxygen reduction are studied by H2-TPR and O2-TPD, respectively. It is discovered for the first time that binary carbonates as ionic conductor mixing with semiconductor homogenously help to form unique semiconducting-ionic microstructure. The particle arrangement and interface conduction in the microstructure significantly influences on the SCFC performances due to different catalytic activity and polarization resistance. Even this, O2 reduction reaction (ORR) for the single homogeneous layer still predominates in the redox reaction and binary carbonates are in favor of the oxygen conduction and desorption. These fin dings are essential to exactly understand the connections among structure, catalytic activities and performances underlying SCFC.