A cobalt‐catalyzed intermolecular 1,2‐difunctionalization of alkenes with anilines/indoles and acetonitrile has been developed. This protocol provides an access to functionalized cyano‐containing molecules. In this transformation, employing di‐tert‐butyl peroxide as a radical initiator, a variety of commercialized nucleophiles and electronically diverse arenes were well tolerated. In addition, we also studied the kinetic isotope effect.