AbstractNon‐noble bimetallic alloys serve as an alternative catalytic material for noble metal‐based catalysts that could be applied in selective hydrogenation of unsaturated compounds. However, maintaining the catalytic stability for bimetallic nanoparticles in the selective hydrogenation process remains a substantial challenge, due to its high tendency to structural transformation upon reactive circumstances. Herein, this problem is solved by constructing carbon‐protected catalytic sites within carbon layer‐coated Ni−Fe nanoalloy composite via pyrolysis of NiFex(OH)2/glucose precursor. The optimized NiFe0.06@C catalyst exhibits excellent stability and selectivity to aminostyrene (>97 %) in the chemoselectivity hydrogenation of 3‐nitrostyrene reaction. Various characterization indicates that the enhancement in stability originates from the protective effect of the carbon layer, which prevents the oxidation and aggregation of Ni−Fe nanoparticles during the reaction process. This work greatly advances non‐noble metal‐catalyzed selective hydrogenation of nitroarenes and helps the rational design of bimetallic catalysts.