An efficient and reusable polyaniline nanofiber supported ferric chloride catalyst was developed and characterized by FT-IR, UV-vis, XPS, TEM and XRD techniques. The catalyst was used in the selective acylation of alcohols and amines employing acetic acid as an acylating agent to obtain the corresponding acetates and acetamides in good to excellent yields. (C) 2008 Elsevier B.V. All rights reserved.