Besides the addition reactions, we further tested the feasibility of performing photocatalytic radical-radical crosscoupling reactions. We started by exploring the C(sp 3 )-H bond arylation reaction of amides (Figure ). Cyanoaromatics 4 are good electron acceptors for generating aryl radical anions as versatile radical coupling partners through decyanation. The results show that our protocol is compatible with various electron-deficient cyanoaromatics (6a -6e) and amides (6f-6l), yielding their corresponding arylated products in good to excellent yields of 30% -96%. Impressively, all cyclic amides (6j -6l) reacted exclusively at its α-N-CH2 position.