Phenols are versatile synthetic intermediates and key structural motifs in many natural products and biologically active compounds. We herein report a visible-light-induced aerobic oxidative hydroxylation of arylboronic acids/pinacol esters using air as oxidant and without using any catalysts and base, etc., additives, providing a green entry to a variety of phenols in a highly efficient and concise fashion. This novel reaction is enabled by photoactivation of an electron donor−acceptor complex, in which THF serves as both the solvent and electron donor. DFT studies indicated that the oxidation process involves a concerted hydrogen abstraction transfer from THF and dehydroxylation of boronic acid undergoing spin crossover from triplet to singlet to produce an active peroxoboronic acid intermidiate. Salient merits of this chemistry include broad substrate scope and excellent functional group tolerance, gram-scale synthesis, and versatile late-stage functionalizations as well as the use of air, visible light, and catalyst-and additive-free conditions. This strategy introduces a novel photoreaction mode with the aid of a solvent, offering a succinct and environmentally sustainable route for synthesizing phenols. The strong practicability and highly efficient access to modifying complex biorelevant molecules bode well for the potential applications of this chemistry in pharmaceutical chemistry.