La0.6Sr0.4Fe0.8Cu0.2O3-δ was prepared via combined EDTA-citrate complexing sol-gel process, characterized by X-ray diffraction and SEM. Ammonia synthesis was successfully synthesized directly from wet nitrogen based on an electrolytic cell using La0.6Sr0.4Fe0.8Cu0.2O3-δ-Ce0.8Gd0.18Ca0.02O2-δ composite cathode, Ce0.8Gd0.18Ca0.02O2-δ-(Li/Na/K)2CO3 composite electrolyte and Sm0.5Sr0.5CoO3-δ-Ce0.8Gd0.18Ca0.02O2-δ composite anode. The O2− conduction of the composite electrolyte was used for ammonia synthesis. The maximum ammonia formation rate of 5 × 10−11 mol s−1 cm−2 was observed at 400°C when a voltage of 1.4 V was applied which is two orders of magnitude higher than that of previous report when ammonia was synthesized from N2 and H2O at 650°C. Besides ammonia, hydrogen is also co-generated at the cathode.