As an ionic conductive functional layer of intermediate temperature solid oxide fuel cells(ITSOFC), samarium-doped ceria(SDC)–Li Na SO4nano-composites were synthesized by a sol–gel method and their properties were investigated. It was found that the content of Li Na SO4 strongly affected the crystal phase, defect concentration, and conductivity of the composites. When the content of Li Na SO4 was 20 wt%, the highest conductivity of the composite was found to be, respectively, 0.22, 0.26, and 0.35 S cm-1at temperatures of 550, 600, and 700 °C, which are much higher than those of SDC. The peak power density of the single cell using this composite as an interlayer was improved to, respectively, 0.23, 0.39, and 0.88 W cm-2at 500, 600, and 700 °C comparing with that of the SDC-based cell. Further, the SDC–Li Na SO4(20 wt%)-based cell also displayed better thermal stability according to the performance measurements at 560 °C for 50 h. These results reveal that SDC–Li Na SO4 composite may be a potential good candidate as interlayer for ITSOFC due to its high ionic conductivity and thermal stability.