The structure, electrical conduction, thermal expansion and electrochemical properties of the La0.6Sr0.4Co0.2Fe0.8O3–δ + La2NiO4+δ (LSCF-LNO) composite cathodes were investigated with regard to the volume fraction of the LNO composition. No chemical reaction product between the two constituent phases was found for the composite cathodes sintered at 1,400 °C for 10 h within the sensitivity of the XRD. Compared to the performance of the LSCF cathode, the LNO composition in the composite cathode plays a role in deteriorating both electrical conductivity and electrochemical properties, however, improving the thermal expansion properties. The trade-off between electrical conducting and thermal expansion classifies the composite cathode containing 30 volume percent (vol.%) LNO as the optimum composition. For characterizing cathode performance in a single cell, a slurry spin coating technique was employed to prepare a porous cathode layer as well as a YSZ/Ce0.8Sm0.2O3–δ (SDC) electrolyte. The optimum conditions for fabricating the YSZ/SDC electrolyte were investigated. The resulting single cell with 70 vol.% LSCF-30 vol.%LNO (LSCF-LNO30) cathode shows a power density of 497 mW cm–2 at 800 °C, which is lower than that of the cell with a LSCF cathode, but still within the limits acceptable for practical applications.