<p>The direct functionalization of inert alkanes is a long-standing challenge in synthetic chemistry owing to the high bond dissociation energy of C(<i>sp</i>³)–H bonds. Hydrogen atom transfer (HAT) has emerged as a powerful strategy for monofunctionalization, while the development of methods enabling vicinal double functionalization of alkanes remains limited and typically relies on a monofunctionalization–β-elimination–difunctionalization cascade. Here we report the development of a double-HAT process, leveraging the distinctive reactivity of photo-generated triplet sulfonyl nitrenes under visible-light irradiation, to directly transform inert alkanes into aziridines. This approach streamlines the synthesis of diverse aziridines from readily available alkanes, with large-scale synthesis assisted by a high-speed circulation flow platform. Mechanistic insights, supported by both experimental and computational investigations, reveal the formation of an olefin intermediate through a double-HAT process, with the in situ-generated triplet sulfonyl nitrenes and iodosobenzene playing critical roles in the reaction pathway.</p><p></p>