Enhancing catalytic performance as well as reducing catalyst cost are the eternal pursuit for the catalysis community. Herein, a simple and effective palladium-doped cobalt (Pd/Co) catalyst with high Pd atom utilization efficiency was synthesized via galvanic replacement reaction for the selective hydrogenation of nitrobenzene with H2 at room temperature, delivering >99 % yield of aniline with up to 158 times higher catalytic activity than commercial palladium powder. Detailed characterizations and DFT calculations revealed that Co-Pd interaction leads to a decrease in electron density of Pd and the distance between Pd atoms that results in the enhanced catalytic performance. Further experiments indicated that the Pd/Co catalyst serves as a highly efficient, selective, and recyclable catalyst for a range of nitroarene substrates. This work might provide a green and sustainable methodology to design and synthesize highly active catalysts with high utilization efficiency of the noble metals in fundamental and applied research.