Catalytic hydrogenation of nitroaromatics is deemed as an environment‐benign strategy to produce industrially important aniline intermediates. Herein, we report that the Pt nanocrystals with Fe(OH) x  deposition, Fe(OH) x  /Pt, enable the selective hydrogenation of nitro group into amino group without hydrogenating other functional groups on aromatic ring. The unique catalytic behavior is identified to be associated with the Fe(III)‐OH‐Pt interfaces. While H 2  activation occurs on exposed Pt atoms to ensure the high activity, the high selectivity towards the production of substituted aniline is originated from the Fe(III)‐OH‐Pt interfaces. In situ  IR, XPS and isotope effect studies reveal that the Fe 3+  /Fe 2+  redox couple facilitates the hydrodeoxygenation of the ‐NO 2  group during hydrogenation catalysis. Benefited from rich Fe(III)‐OH‐Pt interfaces, the Fe(OH) x  /Pt catalysts exhibit high catalytic performance towards a broad range of substituted nitroarenes.