Alkoxy radicals are highly transient species that exhibit diverse reactivity, including hydrogen atom transfer, 1 addition to π systems 2 and β-scission processes (Scheme 1A). The generation of alkoxy radicals directly from aliphatic alcohols is challenging, partly due to the high dissociation energy of RO-H bonds (~105 kcal/mol). As such, traditional methods for alkoxy radical generation involve the homolysis of weak oxygen-heteroatom bonds within pre-functionalized radical precursors in combination with radical initiators and/or thermal or photochemical activation (Scheme 1B). Alternatively, transition metal salts can be employed in combination with stoichiometric oxidants (e.g. K 2 S 2 O 8 or hypervalent iodine reagents) for the generation of alkoxy radicals. Recent advances have developed photocatalytic approaches for alkoxy radical generation employing various radical precursors 5 including peroxides, Nalkoxyphthalimides, N-alkoxypyridiniums, Nalkoxybenzimidazoles, N-alkoxytriazoliums, 10 and unprotected alcohols. Despite these important advances, many existing approaches require the use of pre-functionalized substrates, (super)stoichiometric reagents (generating waste/by-products) and/or precious metal (photo)catalysts.