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The knowledge of redox equilibria of iron in multicomponent molten slags is of significant importance to understand the viscosity, electrical conductivity and structure of iron-containing slags. However, the available data of molar ratio of ferric ion to ferrous ion are limited due to the difficulty of experiment and heavy workload. In this study, a model was established to estimate the XFeO2−/XFe2+$${{{X_{{\rm{FeO}}_2^ -}}} \mathord{\left/{\vphantom {{{X_{{\rm{FeO}}_2^ -}}} {{X_{{\rm{F}}{{\rm{e}}^{2 +}}}}}}} \right. \kern-\nulldelimiterspace} {{X_{{\rm{F}}{{\rm{e}}^{2 +}}}}}}$$ (normally, most of ferric ions exist in the form of complex anions such as FeO2−$${\rm{FeO}}_2^ - $$) ratio in CaO–MgO–Al2O3–SiO2–“FeOt” slags, which can give good estimation results compared to the experimental measured values. From the model, by increasing oxygen partial pressure or decreasing temperature, the XFeO2−/XFe2+$${{{X_{{\rm{FeO}}_2^ -}}} \mathord{\left/{\vphantom {{{X_{{\rm{FeO}}_2^ -}}} {{X_{{\rm{F}}{{\rm{e}}^{2 +}}}}}}} \right. \kern-\nulldelimiterspace} {{X_{{\rm{F}}{{\rm{e}}^{2 +}}}}}}$$ ratio will increase. Different components have different influences on XFeO2−/XFe2+$${{{X_{{\rm{FeO}}_2^ -}}} \mathord{\left/{\vphantom {{{X_{{\rm{FeO}}_2^ -}}} {{X_{{\rm{F}}{{\rm{e}}^{2 +}}}}}}} \right. \kern-\nulldelimiterspace} {{X_{{\rm{F}}{{\rm{e}}^{2 +}}}}}}$$ ratio: CaO and MgO are beneficial for the increase of this ratio, but Al2O3 and SiO2 have reverse effects.