A microscopic site binding model to treat binding of several metal ions to multi-center receptors is proposed. The model introduces the appropriate parameterization in terms of microscopic complexation constants and metal–metal pair interaction energies. The model is solved with statistical mechanical techniques, including direct enumeration or transfer matrices. We obtain microscopic and macroscopic complexation constants, microstate probabilities, and binding isotherms for chain-like receptors, including the long-chain limit. Various examples to illustrate the usefulness of the model are given.