Functionalization of C(sp3)-H bonds represents the most straightforward and atom-economical transformation in organic synthesis. An innovative approach integrating photocatalytic hydrogen atom transfer (HAT) and transition metal catalysis has made significant progress in the coupling of α-heterosubstituted C-H bonds with alkyl halides. However, unactivated alkanes were ineffective as a result of the preponderance of byproduct formation. Herein, we demonstrate direct HAT and nickel catalysis in the coupling of cycloalkanes and benzyl bromides/primary alkyl iodides. Additionally, tetrabutylammonium decatungstate (TBADT) was recovered and recycled.