Poly(4-vinylpyridine) perchlorate, is a supported, recyclable, eco-benign catalyst for the reaction acetylation of structurally diverse alcohols, phenols and amines at room temperature under solvent-free conditions. The catalyst was studied by FT-IR. X-ray diffraction, Scanning Electron Microscope and Thermo-gravimetric Analyses. All the products were extensively characterized by H-1 NMR, FT-IR, GC-MS and melting point analyses. The catalyst can be recovered and reused without loss of activity. The workup of the reaction consists of a simple filtration, followed by concentration of the crude product and purification. It is important to point out that a large-scale reaction is possible using a same amount of catalyst. (C) 2012 Elsevier B.V. All rights reserved.