A Minisci-type δ-selective C(sp)-H heteroarylation of sulfonyl-protected primary aliphatic amines with -heteroarenes under photoredox-catalyzed conditions was developed. The reaction typically uses a slight excess of amine reactant. The use of benziodoxole acetate (BI-OAc) oxidant and hexafluoroisopropanol solvent is critical to achieve high yield. Besides methylene C-H bonds, heteroarylation reactions of δ methyl C-H bonds also worked under more forced conditions. The reactions show a broad scope for both amine and -heteroarene substrates, offering a straightforward method for synthesis of complex δ-heteroarylalkylmines from simple precursors.