A mild, practical method for direct arylation of unactivated C(sp3)-H bonds with heteroarenes has been achieved via photochemistry. Selectfluor is used as a hydrogen atom transfer reagent under visible light irradiation. A diverse range of chemical feedstocks, such as alkanes, ketones, esters, and ethers, and complex molecules readily undergo intermolecular C(sp3)-C(sp2) bond formation. Moreover, a broad array of heteroarenes, including pharmaceutically useful scaffolds, can be alkylated effectively by the protocol presented here.