Single-atom alloys hold great promise for electrocatalytic nitrogen reduction reaction (NRR), while the comprehensive experimental/theoretical investigations of SAAs for the NRR are still missing. Herein, PdFe 1 single-atom alloy metallene, in which the Fe single atoms are confined on a Pd metallene support, is first developed as an effective and robust NRR electrocatalyst, delivering exceptional NRR performance with an NH 3 yield of 111.9 μg h À 1 mg À 1 , a Faradaic efficiency of 37.8 % at À 0.2 V (RHE), as well as a long-term stability for 100 h electrolysis. In-depth mechanistic investigations by theoretical computations and operando X-ray absorption/Raman spectroscopy indentify Pdcoordinated Fe single atoms as active centers to enable efficient N 2 activation via N 2 -to-Fe σ-donation, reduced protonation energy barriers, suppressed hydrogen evolution and excellent thermodynamic stability, thus accounting for the high activity, selectivity and stability of PdFe 1 for the NRR.