An efficient approach for C–N bond construction by the coupling reaction of arylsulfonyl hydrazides and C_sp2–X compounds is described for the first time with good yields at room temperature. The reaction promoted by the simple base DMAP displays excellent regioselectivity as well as high functional group tolerance with 41 examples. Even for inactive C_sp2–Cl compounds, the metal-free transformation also affords a satisfactory yield after prolonging the reaction time, which is comparable to that of the corresponding C_sp2–Br compound. The good effect of DMAP and its action mechanism are confirmed by the competitive experiments of reactivity between Cl-substituted and Br-substituted substrates and the single-crystal X-ray analysis of the key intermediate quaternary ammonium salt. Importantly, the application of this method for a gram-scale (even over 10 g) preparation can be accomplished.