Versatile Photocatalytic Oxidation Enabled by a Tetraphenylethylene‐Based Supramolecular System

Artificial systems that efficiently utilize light offer a viable approach for photocatalytic oxidation under mild conditions. Herein, the photocatalytic performance of a tetraphenylethylene‐based supramolecular system is investigated. The assembled system (TPEC/CTAB‐ESY‐SR101) enables multiple oxidation reactions with high efficiency. Aryl sulfides are selectively converted to sulfoxides in up to 99% yield via singlet oxygen ( 1 O 2 ), while phenylboronic acids are oxidized to phenols in up to 90% yield, predominantly mediated by superoxide radicals (O 2 •− ). In addition, lignin photodegradation is significantly enhanced from 35% for TPEC alone to 82% in the assembled system. This work demonstrates a versatile supramolecular platform that integrates efficient reactive oxygen species generation with diverse photocatalytic oxidation reactions, providing a practical strategy for solar‐driven oxidation chemistry.