Designing efficient noble metal‐free catalysts for plasma‐catalytic ammonia synthesis is significant and challenging. Carbon‐based metal catalysts were prepared at different pyrolysis temperatures using the Ni‐MOF‐74 precursor. The effects of Ni‐MOF‐74 and its derived carbon‐based metal catalysts on pulsed dielectric barrier discharge (DBD) plasma ammonia synthesis were investigated. The results showed that Ni‐MOF‐74‐300 with both the MOF structure and nickel metal particles exhibited the best catalytic performance for ammonia synthesis. The ammonia synthesis rate reached 41.38 mmol g−1 h−1, whereas the nitrogen conversion rate was as high as 1.54% with an energy yield of 3.04 g kWh−1. Compared to the situation of plasma only, the ammonia synthesis rate, nitrogen conversion rate, and energy yield were increased by 28.46 times, 5.7 times, and 5.5 times, respectively.