The development of active and selective catalysts based on non-precious metals for the chemoselective reduction of nitro compounds, which can work under mild conditions in Aquomedien, is an attractive research area. The synthesis of subnanometric and stable cobalt nanoclusters on N-doped carbon supports (Co @ NC-800) for the chemoselective reduction of nitroarenes is described here. The Co @ NC-800 catalyst was prepared by pyrolysis of the Co (tpy) 2 complex impregnated on volcanic carbon. Indeed, the use of a molecular complex based on six N-Co boundaries results in the formation of a well-defined and distributed cobalt core-shell nanocluster over N-doped carbon. To elucidate its nature, this has been fully characterized through the use of several advanced techniques. In addition, this catalyst produced in this way showed a high activity, chemoselectivity and stability towards the reduction of nitro compounds with H 2 under mild reaction conditions and water as the green solvent, whereby the results previously based on cobalt catalysts were improved. In addition, the Co @ NC-800 catalyst is also active and selective for the one-pot synthesis of secondary arylamines and isoindolinones by reductive amination of nitroarenes. Finally, based on diffraction and spectroscopic investigations, metallic cobalt nanoclusters with surface CoNx patches were proposed as the active phase in Co @ NC-800 material.