An organophotocatalyzed approach for the chemoselective dealkylation of phenols is developed. This method demonstrates exceptional selectivity toward the cleavage of phenolic ethers over equivalent aliphatic ethers and alkyl benzoates, presenting a broad range of functional group sustainability. This strategy also enables selective debenzylation of phenols in the presence of reduction-sensitive functional groups. Mechanistic studies and photophysical experiments provide evidence for the selective disintegration of C-O bonds through photo-oxidation, facilitated by the oxophilicity of silicon.