We have developed an efficient palladium-catalyzed denitrative N-arylation via cross-coupling of N–H heteroarenes with nitroarenes, one of the most inexpensive and fundamental feedstocks in the chemical industry. A variety of functionalized N-arylated heterocycles could be selectively synthesized in moderate to excellent yields. Furthermore, the success of the scale-up experiment and application in the late-stage modification of natural products and pharmaceutical derivatives showcased the synthetic potential of the direct denitrative N-arylation protocol in synthetic chemistry.