A novel pyridinium salt-supported [hydroxy(tosyloxy)-iodo]benzene (HTIB) reagent (N-{4-[hydroxy(tosyloxy)iodo]-phenyl}pyridinium hexafluorophosphate) was prepared via Zincke's reaction. The conjugated HTIB was an effective reagent for tosyloxylation of phenolic aromatic rings with an electron-withdrawing substitute at the ortho-position. The reagent can be easily regenerated in high yield and reused three times without any decrease in activity.