Heteroatom-doped carbon nanomaterials are effective metal-free catalysts for organic reactions. However, S-doped carbocatalysts are relatively unexplored due to challenges related to the synthesis of S-doped nanocarbon. Herein, we employed a facile, low-cost and eco-friendly approach to construct a N,S co-doped hierarchical carbon nanomaterial (NSHC) via the pyrolysis of an azo-sulphonate dye pollutant intercalated layered double hydroxide. The as-prepared NSHC possesses a two-dimensional hierarchical porous structure with ultrathin carbon nanosheets uniformly distributed on hexagonal carbon nanoplates, endowing the material with a high specific surface area of 1260 m2 g-1. Attributed to the synergistic effects of N,S co-doping, the high specific surface area and the interconnected porous architecture, NSHC demonstrates excellent catalytic activity and selectivity in the reduction of nitroarenes. Among the reported carbocatalysts for nitrobenzene reduction using hydrazine hydrate, NSHC shows the highest turnover frequency value of 4.89 h-1. Furthermore, NSHC exhibits remarkable recyclability and generality for the reduction of various aromatic nitro compounds.