Our previous strategy of forming C-, S-, and Ncentered radicals with photoexcited catalysts and engaging them in Ni-catalyzed cross-couplings is not amenable to C-O cross-coupling. Unlike carboxylates, thiols, and anilines, the high oxidation potentials of alcohols preclude them from the oxidation process with available photocatalysts. As detailed by Hillhouse and others, singlet state Ni(II) heteroatomic complexes tend not to undergo reductive elimination. However, SET oxidation of a Ni(II) Ar-heteroatomic complex or an EnT-induced excitation to its triplet state would promote reductive elimination (Figure ). Triplet-triplet EnT is a powerful activation pathway in photocatalysis that unlocks new organic transformations and improves the efficiency of metal-catalyzed cross-couplings. Many current reports, however, still rely on precious metal-based complexes as EnT photosensitizers, with associated prohibitive costs and environmental impacts (Figure ). We recognized that photosensitizers exhibiting thermally activated delayed fluorescence (TADF) could be an attractive fully organic alterna- .9 kcal/mol), which is a requirement for an EnT process (Figure ). The dual catalytic cycles are illustrated in Figure .