Bismuth ferrite (BiFeO3) nanopowder was prepared by the novel combustion technique using sucrose as a fuel.The catalyst was characterized by using XRD, FT-IR, scanning electron microscope (SEM), transmission electron microscope (TEM), and BET surface area measurement and used as the heterogeneous catalyst for the acetylation reaction under solvent-free conditions. Efficient and selective acetylation of various amines, alcohols and phenols was carried out over BiFeO3 nanopowder by using acetic anhydride and/or acetyl chloride as the acetylating agents at room temperature under solvent-free conditions. The method is highly chemoselective-alcoholic hydroxyl group can be protected while phenolic hydroxyl group remains intact and the amine group can be acetylated in the presence of hydroxyl. This method is fast, high yielding, clean, safe, cost effective, compatible with the substrates having other functional groups and very suitable for practical organic synthesis. The catalyst can also be reused for acetylation without loss of catalytic activity. (C) 2008 Elsevier B.V. All rights reserved.