Air-stable titanocene bis(perfluorooctanesulfonate) [Cp 2Ti(OSO 2C 8F 17) 2] that shows high Lewis acidity was prepared from Cp 2TiCl 2 and AgOSO 2C 8F 17. The compound was characterized by different techniques, and examined as a catalyst for acylation reactions. It was found that using equimolar acetic anhydride as acetylating agent and under solvent-free condition, Cp 2Ti(OSO 2C 8F 17) 2 exhibits high activity and selectivity in the acetylation of various alcohols, phenols, thiols, and amines. Also, good catalytic efficiency is observed in the acylation of 2-phenylethanol across various acylating reagents. The catalyst can be reused without loss of activity in a test of ten cycles. The Cp 2Ti(OSO 2C 8F 17) 2 catalyst affords a simple, efficient and general method for the acylation of alcohols, phenols, thiols, and amines.