The functionalization of unactivated C(sp3)-H bonds poses a significant challenge due to their ubiquity and relative similarity in most organic frameworks. Herein, we describe the use of a combined photoredox and nickel catalytic system for the regioselective C(sp3)-C(sp3) coupling of unactivated C(sp3)-H bonds and alkyl bromides. Positional selectivity is dictated by a 1,5-hydrogen atom transfer (HAT) reaction by a pendent amide. Interception of this radical by a Ni catalyst allows distal alkylation to occur in good yield and excellent selectivity.