Organic ligands, such as EDTA, accelerate the dissolution of silicate and oxide minerals. In natural systems, oxyanions can compete with organic ligands for mineral surface sites thereby affecting ligand-promoted dissolution rates, either enhancing or inhibiting dissolution, depending upon pH. The influence of selenite, molybdate and phosphate on the EDTA-promoted dissolution of goethite has been examined and a mechanism proposed for the observed differences in dissolution rates over a pH range of 4–8. We propose that the surface complex formed by EDTA is the controlling factor for the observed dissolution rate, with mononuclear complexes accelerating dissolution compared to bi- or multinuclear complexes. Dissolution results from our experiments suggest that EDTA forms multinuclear complexes at pH values ≥6 and mononuclear complexes at pH values <6. Dissolution results show that when the oxyanion and the EDTA are present in the system at concentrations nearly equalling the surface sites available for adsorption, the oxyanion reduces the adsorption of EDTA and inhibits dissolution. However, if the oxyanion is present at lower concentrations at pH values ≥6, EDTA is adsorbed but the number of carboxylic groups that can bind to the surface is reduced causing the formation of mononuclear complexes. This shift to a weaker surface complex enhances the EDTA-promoted dissolution of goethite in the presence of the oxyanions compared to EDTA-promoted dissolution in their absence.