A series of N-enriched active carbons (NACs) were prepared from carbonization of tobacco stem with KOH as activating agent. The obtained NACs were used as efficient metal free catalysts for reduction of nitroarene. The results of N2 adsorption–desorption indicate that NACs have a large number of mesopores with the increase of mass ratio of KOH to the precursor. NACs-3800 has high surface area (SBET = 2938 m2 g−1) and a large pore volume (Vtotal = 1.60 cm3 g−1) with a nitrogen content (1.32%). NACs-3800 showed a high catalytic activity (99.9% conversion, nearly 100% selectivity to aniline) in the reduction of nitrobenzene. Moreover, NACs-3800 also exhibits good catalytic activity in the reduction of substituted nitroarenes. Furthermore, the NACs-3800 presented remarkable activity and durability for nitrobenzene reduction to the corresponding aniline. The recyclability of the catalyst and its cheap feedstock makes the overall process much simple, cost-efficient and environment-friendly.