A method for electrooxidative C(sp3)–H amination via intermolecular oxidative C(sp3)–H/N–H cross-coupling has been developed under metal- and oxidant-free conditions. The C(sp3)–H bonds adjacent to oxygen, nitrogen, and sulfur atoms could all react smoothly with various amines to give the corresponding products with moderate to good yields (30–93%). In addition, the C(sp3)–H bonds of benzylic and allylic are also tolerated in this reaction. A preliminary mechanistic study indicates that the C–H cleavage of tetrahydrofuran is probably not involved in the rate-determining step.