[FeIII(TF4DMAP)Cl] can efficiently catalyze intermolecular sp3 C-H amination using aryl azides and intramolecular sp3 C-H amination of alkyl azides in moderate-to-high product yields. At catalyst loading down to 1 mol %, the reactions display high chemo- and regioselectivity with broad substrate scope and are effective for late-stage functionalization of complex natural/bioactive molecules.