Herein, we report a regioselective, photocatalytic C3 α-aminoalkylation of coumarins via a cross-dehydrogenative coupling of dimethylanilines and coumarins. Molecular oxygen was utilized as the oxidizing agent in this transformation, which exhibits a wide substrate scope and affords the products in good yields. It was established that 4-amino-substituted coumarin reacts via a different mechanism compared to coumarin derivatives that are unsubstituted at the 4-position.