Copper oxide (CuO) is used as a reusable solid reagent for hydrogenation of nitroarenes to aminoarenes. The use of CuO resulted in 100 % conversion of 2.9 mmol of nitrobenzene to aniline in 45 s at room temperature using hydrazine hydrate as the reducing agent. During the reaction, CuO is converted to inactive metallic Cu which can be regenerated to active CuO by thermal oxidation. DFT simulations indicated facile formation of oxygen vacancies (EO,vac = −3.8 kJ/mol) on the surface of CuO (111) in reducing environment which is consistent with the XPS analysis. Oxygen vacancies facilitate stronger nitrobenzene binding (−148.5 kJ/mol) and reduced activation barrier (Ea = 36.4 kJ/mol) for N[sbnd]O dissociation. Motivated from this mechanistic insight -NO2 groups in various nitroarenes were selectively hydrogenated to [sbnd]NH2 groups using CuO. © 2021 Elsevier B.V.