Direct cross coupling with C(sp3)–H bonds presents a significant challenge in organic synthesis, typically requiring directing groups, a large excess of the C–H partner, or forcing reaction conditions. We have reported examples of selective cross coupling of the α-amino C(sp3)–H bonds of acyclic and cyclic anilines with aryl halides and anhydrides using a nickel-photoredox dual catalyst system. More recently, we have pursued C(sp3)–H cross coupling of ethers and unactivated alkanes enabled by photocatalysis at nickel. In particular, photolysis of Ni(III) aryl and acyl chloride intermediates leads to elimination of a chlorine radical that can mediate substrate activation via HAT. Using this strategy, our lab has reported etherification, formylation, and methylation reactions of (hetero)aryl chlorides, in addition to esterification of strong and entirely unactivated C(sp3)–H bonds.