Herein, we report an azobis(isobutyronitrile) (AIBN)promoted radical α-cyanation of in situ formed imine under atmospheric O 2 . This oxidative radical addition (ORA) procedure proceeds with the sequential homocleavage of AIBN, extrusion of N 2 , and capture of O 2 toward an Ocentered radical, which is converted to a cyano radical by β-scission. Then, the insertion of the cyano radical into the imine C�N bond forms an aminyl radical, leading to α-cyano imine after 1,2-hydrogen atom transfer (HAT) and H abstraction. Such a transition-metal-free procedure features mild reaction conditions and a broad substrate scope, employing molecular O 2 as a clean terminal oxidant.