Abstract An I 2 /cumene hydroperoxide (CHP)‐mediated tandem cyclization of 2‐aminoaryl ketone oximes with isocyanides has been developed. Various 2‐aminoquinazolines were obtained in 49–96% yields under transition‐metal‐free conditions, and the resulting 4‐phenylquinazolin‐2‐amines show typical fluorescent emission properties. The key to the success of this strategy involves the formation of iminyl radical via the N−O bond cleavage of hydroxy oxime.