Previously obtained data for redox equilibria of metal ion couples in molten silicates indicate dependence on melt basicity. Treating these data in the context of the optical basicity model allows the prediction of redox equilibria for ion couples simply from standard electrode potentials, E(0), in aqueous solution. The method is extended to obtain electrode potentials for 25 metal/metal ion couples in the melts and to show the effect of basicity changes (through compositional adjustments, for example). Experimental data, from voltametric studies in silicate melts, are available for nine of the metal/metal ion couples, and they show reasonably good agreement with the electrode potentials predicted from the optical basicity values of the melts. In the basicity region of interest to the glass maker, the results show an electrochemical series which is somewhat different from that in aqueous solution. Increasing melt basicity causes a decrease in the difference between the electrode potentials, but little change in the series. The difference almost disappears for basicities where the silicate network is undergoing large-scale disruption to individual SiO44- units. This basicity region corresponds to the composition of metallurgical slags used in steel making.