A 1,10-phenanthroline-type bifunctional ligand has been developed for Cu catalyzed direct γ-C(sp3)-H amination with intermolecular anilines. Stabilizing N-centered radicals via amide group installed on the bifunctional ligands, a new catalytic system for site-selective γ-C(sp3)-H amination to synthesize p-aminophenols was established. The economical and practical approach by using oxygen as the terminal oxidant was mild and environmental friendly.