Abstract Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr‐TPDCS‐1, consisting of Zr6‐clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′‐tetramercapto1,1′:4′,1′′‐terphenyl‐4,4′′‐dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr6‐cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram‐scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl‐radical catalysis.
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