Reported herein is the design and development of a new photo-induced amidation protocol with the readily available N-chlorosulfonyl carbamate as an effective amidyl-radical precursor, which could be readily prepared from commercial low-cost chlorosulfonyl isocyanate (CSI) and alcohol feedstocks. The synthetic potency of this developed protocol was well demonstrated by direct amidation of various quinoxalin-2(1H)-ones. The protocol could be further streamlined by implementing a one-pot/two-step/three-component process of CSI, alcohol, and quinoxalin-2(1H)-one, with significantly improved reaction efficiency. This methodology offers an intriguing opportunity for rapid expansion of nitrogen-containing molecular complexity, thus inspiring comprehensive exploration of a new reaction mode of CSI reagent.