Quantum-mechanical calculations have been performed to investigate the crystal structure and the nature of chemical bonding in Li2I(OH). All simulations have been carried out using the density functional approach. The structural parameters have been optimized and their good agreement with the experimental data has been demonstrated. Computed topological properties of the electron density at the bond critical points and also the AIM charges reveal the dominant role of closed-shell interaction in this compound. The nature of the bonding in Li2I(OH) was also discussed on the basis of an analysis of the electron localization function (ELF). (C) 2003 Elsevier Science B.V. All rights reserved.