AbstractA supramolecular organic framework‐type photocatalyst, named TM‐SOF, is constructed by the self‐assembly of cucurbit[8]uril and a tetra‐arm monomer containing four N, N’‐dimethyl 2,5‐bis(4‐pyridinium)thiazolo[5,4‐d]thiazole (MPT) moieties. Benefiting from the multivalent assembly, a photocatalytically active supramolecular MPT dimer can be stably formed in TM‐SOF. In addition, TM‐SOF exhibits better stability against temperature, substrate, and light irradiation. As a result, TM‐SOF shows a significantly improved performance for the photocatalytic aerobic oxidation of aryl boronic acids and thioethers. It is anticipated that this line of research will provide a facile approach for fabricating high‐performance supramolecular photocatalysis systems.