A novel one-step direct reductive coupling reaction between nitroarenes and sodium arylsulfinates was realized in the presence of an inexpensive Pd/C catalyst. In this procedure, readily available nitroarenes are employed as the nitrogen sources, and sodium arylsulfinates serve as both coupling partners and reductants. The method features high efficiency by using cheap Pd/C with low catalyst loading and good functional group tolerance in the absence of any additional reductants or ligands. This facile and mild synthetic method enables the high efficiency synthesis of functionalized N-arylsulfonamides from readily available substrates.