In this study, possible leaching control mechanisms for Cr and V in electric arc furnace slags were investigated by using a multi-methodological approach. Aside from chemical and mineralogical bulk analyses, special emphasis was given to surface investigations of the slags prior to and after leaching. In addition, pH dependence leaching tests were performed and the obtained data were evaluated with hydrogeochemical models. Investigations revealed that Cr and V are mainly bound in spinel and wuestite as well as minor amounts of olivine. Spinel and wuestite do not dissolve during water leaching for 48 h, whereas, depending on the composition of olivine, this phase either dissolves and releases V and Cr congruently, or does not dissolve but may hydrate. Melilite may also hydrate, but neither V nor Cr were detected in this phase. It appears that leached V is subsequently adsorbed onto these newly hydrated phases. The combination of the applied methods further showed that the abundance of calcium silicates, spinel, and wuestite is influenced by the FeO/SiO ₂ and CaO/SiO ₂ ratio in the slag. Therefore, it is assumed that the leaching of V and Cr can be minimized by changing these ratios to favor the formation of Fe bearing calcium silicate and spinel instead of wuestite.