An in situ generated photoactive copper(I)‐complex‐catalyzed aziridination reaction of cyclic N‐sulfonyl imines with α‐aryl‐substituted vinyl azides irradiated by blue‐LEDs light is reported for the first time. This novel SET process represents a mild, sustainable, and pragmatic method for accessing synthetically resourceful sulfamidate‐fused aziridines in acceptable chemical yields with excellent diastereoselectivities. Delightedly, pharmacologically attractive benzo[f][1,2,3]oxathiazepine dioxides and fused isoxazoline frameworks were achieved through our newly developed metal‐free based ring‐expansion techniques, highlighting the synthetic value of accessed aziridines. Finally, the possible mechanism for [2+1] aza‐cyclization was presented based on the conduction of a series of control experiments.