Achieving more meaningful N₂ conversion by reducing the energy input and carbon footprint is now being investigated through a method of N₂ fixation instead of the Haber–Bosch process. Unfortunately, the electrochemical N₂ reduction reaction (NRR) method as a rising approach currently still shows low selectivity (Faradaic efficiency < 10%) and high-energy consumption [applied potential at least − 0.2 V versus the reversible hydrogen electrode (RHE)]. Here, the role of molybdenum aluminum boride single crystals, belonging to a family of ternary transition metal aluminum borides known as MAB phases, is reported for the electrochemical NRR for the first time, at a low applied potential (− 0.05 V versus RHE) under ambient conditions and in alkaline media. Due to the unique nano-laminated crystal structure of the MAB phase, these inexpensive materials have been found to exhibit excellent electrocatalytic performances (NH₃ yield: 9.2 µg h⁻¹ cm⁻² mg _cat. ⁻¹ , Faradaic efficiency: 30.1%) at the low overpotential, and to display a high chemical stability and sustained catalytic performance. In conjunction, further mechanism studies indicate B and Al as main-group metals show a highly selective affinity to N₂ due to the strong interaction between the B 2p/Al 3p band and the N 2p orbitals, while Mo exhibits specific catalytic activity toward the subsequent reduction reaction. Overall, the MAB-phase catalyst under the synergy of the elements within ternary compound can suppress the hydrogen evolution reaction and achieve enhanced NRR performance. The significance of this work is to provide a promising candidate in the future synthesis of ammonia.