The extraction of copper(II) and zinc(II) from acidic chloride solutions with protonated Kelex 100 (HL) was studied and the extraction isotherms were determined for systems containing individual metal ions and their mixtures. A chemical model was proposed and verified. It considers the coextraction of the following species: MCl4(H2L)(2), MCl4(H2L)(2). HCl, MCl3(H2L), ML2, and H2L . HCl. Zinc(II) is extracted as the metal ion pairs, while copper(II) can be extracted as the metal ion pair and the chelate. The model can be used to predict the effect of experimental conditions on extraction and coextraction of the metal ions considered.