The development of highly efficient and cost-effective nonprecious metal catalysts for the selective hydrogenation of halogenated nitroarenes is very appealing yet challenging. Here, we demonstrate that the hydrogenation activity and selectivity of Co single-atom catalyst (SAC) can be tuned by tailoring the structure of second coordination sphere via P doping. As revealed by synchrotron radiation-based X-ray absorption spectroscopy characterizations, such a P doping on N-coordinated Co SAC results in the unsymmetric Co-N4P1 coordination structure. With a combination of experimental characterizations and theoretical simulations, we find that tailoring the second coordination sphere can greatly improve H2 dissociation and product desorption. As a result, the Co-N4P1 SAC exhibits superior activity, selectivity and stability for the hydrogenation of halogenated nitroarenes to corresponding amines (20 examples, >99% yields) at 80 oC under 0.5 MPa H2 pressure, significantly outperforming most heterogeneous catalysts reported in the literature. We expect that this work opens a new avenue for the design of highly efficient nonprecious metal SACs for important hydrogenation reactions.