A variety of strategies for direct alkoxylation of the benzyl C-H bond have been developed toward the construction of benzyl ethers. The light-induced benzyl C-H bond alkoxylation provides an alternative strategy for the synthesis of these important intermediates. The photocatalyzed alkoxylation of the benzyl C-H bond has dominated by metal-catalyzed methods. Herein, we reported a light-driven organocatalytic approach for alkoxylation of the benzyl C-H bond by the use of 9,10-dibromoanthracene as a photocatalyst and employing N-fluorobenzenesulfonimide as an oxidant. This reaction proceeds at room temperature and is capable of converting a variety of alkyl biphenyl and coupling partners, including a variety of alcohol and carboxylic acid, as well as peroxide, to the desired products under 400 nm light irradiation.