Triple perovskite has been recently developed for the intermediate temperature solid oxide fuel cell (IT-SOFC). The performance of Nd1.5Ba1.5CoFeMnO9−δ (NBCFM) cathodes for IT-SOFC is investigated in this work. The interfacial polarization resistance (RP) of NBCFM is 1.1273 Ω cm2~0.1587 Ω cm2 in the range of 700–800 °C, showing good electrochemical performance. The linear thermal expansion coefficient of NBCFM is 17.40 × 10−6 K−1 at 40–800 °C, which is significantly higher than that of the electrolyte. In order to further improve the electrochemical performance and reduce the thermal expansion coefficient (TEC) of NBCFM, Ce0.8Sm0.2O2−δ (SDC) is mixed with NBCFM to prepare an NBCFM-xSDC composite cathode (x = 0, 10, 20, 30, 40 wt.%). The thermal expansion coefficient decreases monotonically from 17.40 × 10−6 K−1 to 15.25 × 10−6 K−1. The surface oxygen exchange coefficient of NBCFM-xSDC at a given temperature increases from 10−4 to 10−3 cm s−1 over the po2 range from 0.01 to 0.09 atm, exhibiting fast surface exchange kinetics. The area specific resistance (ASR) of NBCFM-30%SDC is 0.06575 Ω cm2 at 800 °C, which is only 41% of the ASR value of NBCFM (0.15872 Ω cm2). The outstanding performance indicates the feasibility of NBCFM-30% SDC as an IT-SOFC cathode material. This study provides a promising strategy for designing high-performance composite cathodes for SOFCs based on triple perovskite structures.