A low-cost, green catalyst for nitrobenzene (NB) hydrogenation is needed for aniline production. We report the preparation of highly-dispersed Co particles supported on N-doped carbons by the hydrothermal treatment of glucose, followed by the pyrolysis of a mixture of urea, glucose hydrochar and cobalt nitrate in one-pot. The effect of the pyrolysis temperature on the microstructure of the catalysts was studied. Results indicated that the activity for NB hydrogenation was highly affected by the surface area, Co-loading level and Co-Nx coordination in the catalysts. Co@NCG-800 pyrolyzed at 800 °C with 10% Co in the precursor had extraordinary activity for NB hydrogenation, achieving full conversion and 99% aniline selectivity in isopropanol at 100 °C and 1 MPa H2 pressure for 2.5 h. NB conversion and aniline selectivity over the catalysts remained almost unchanged after six recycles, due to the strong coordination between the N- and Co-species. The reaction system showed not only a high NB activity but also a green and durable catalytic process, with easy operation, easy separation and catalyst reusability.