The molecular cluster model approach for the description of processes at surfaces is presented. It involves using finite clusters that contain surface atoms interacting with atomic or molecular adsorbates. Accurate ab initio wave functions can be obtained for the clusters, and, thus, this makes it possible to describe the bonding in terms that are familiar for molecular systems. The adsorbate‐substrate interaction can be analyzed by new techniques developed to characterize the bonding as covalent or ionic. This is shown for F on Ag(111) and O and CO on Cu(100) systems. The measures of adsorbate ionicity are (a) the expectation value of a projection operator giving an indication of the number of electrons associated with the adsorbate, (b) the analysis of the dipole moment curve as function of the distance, and (c) the effect of an external electric field on the adsorbate geometry. The consequences of ionic adsorbates on metal surfaces is discussed for two selected topics: adsorption of thiocyanate on Ag electrodes and coadsorption of CO with ionic species. Copyright © 1990 John Wiley & Sons, Inc.