Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp3)-H bonds and thereby convert feedstock alkanes into value-added fine chemicals. Nevertheless, the high reactivity of HAT reagents, coupled with the small differences among various C(sp3)-H bond strengths, renders site-selective transformations of straight-chain alkanes a great challenge. Here, we present a photocatalytic intermolecular radical sampling process for the iron-catalyzed borylation of terminal C(sp3)-H bonds in substrates with small steric hindrance, including unbranched alkanes. Mechanistic investigations have revealed that the reaction proceeds through a reversible HAT process, followed by a selective borylation of carbon radicals. A boron-sulfoxide complex may contribute to the high terminal regioselectivity observed.