<p>In this work, iodine-doped reduced graphene has been prepared via simultaneous iodine doping and reduction of graphene oxide by a facile heat treatment method. The iodinated graphene was characterized using Fourier-transform infrared spectroscopy, X-ray diffraction analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy techniques. Iodine was demonstrated to incorporate into graphene network in the form of triiodide and pentaiodide. The applicability of the prepared iodine-doped reduced graphene was demonstrated for the protection of the hydroxyl group. Various carbohydrates, alcohols, and phenols were subjected to the acetylation reaction using acetic anhydride in the presence of a catalytic quantity of iodine-doped reduced graphene under solvent-free conditions at room temperature. The catalytic method described has a wide range of applications, proceeds under mild conditions, and the resulting products are obtained in high yields within a short reaction time. The catalyst shows high stability and can be reused without any considerable loss of activity.</p> Graphical abstract <p></p>