As an alternative approach for N2 fixation under milder conditions, electrocatalytic nitrogen reduction reaction (NRR) represents a very attractive strategy for sustainable development and N2 cycle to store and utilize energy from renewable sources. However, the research on NRR electrocatalysts still mainly focuses on noble metals, while, high costs and limited resources greatly restrict their large‐scale applications. Herein, as a proof‐of‐concept experiment, taking PdCu amorphous nanocluster anchored on reduced graphene oxide (rGO) as NRR catalysts, the optimum Pd0.2Cu0.8/rGO composite presents a synergistic effect and shows superior electrocatalytic performance toward NRR under ambient conditions (yield: 2.80 µg h−1 mgcat.−1 at −0.2 V vs reversible hydrogen electrode), which is much higher than that of monometallic, especially noble metal, counterparts. The superior catalytic performance of alloy catalysts with low noble metal loading would strongly spur interest toward more researches on NRR catalysts in the future. PdCu amorphous nanoclusters anchored on graphene are successfully synthesized by a facile coreduction route. The optimum Pd0.2Cu0.8/rGO sample presents enhanced electrocatalytic performance toward electrochemical N2 fixation to NH3 under ambient conditions.