Ferric-rich calcium sulfoaluminate (FR-CSA) cement is a type of low-carbon cement. Common CSA needs to consume a large number of bauxite during the preparation process. In FR-CSA, Fe2O3 can act as an alternative for Al2O3 by shaping some iron-bearing minerals (Ca4Al2Fe2O10 (C4AF), Ca2Fe2O5 (C2F), and Ca4Al6−2xFe2xSO16 (C4A3-xFxS-)). In order to reduce the use of Al2O3 and optimize the iron-bearing mineral compositions in the FR-CSA clinker, this study investigated the effect of CaSO4 batching in raw material on the formation of C4AF and C4A3-xFxS- at 1250 °C. It was proved that CaSO4 plays an important role and the maximum incorporation amount of Fe2O3 could be 16.18 wt% in C4A3-xFxS-, thereof x in the subscripts being 0.33. With the CaSO4 contents in the targeted clinker increasing from 0 to 10 wt%, the effective utilization rates of both Al2O3 and Fe2O3 significantly increased. When the excess amount of CaSO4 was >10 wt%, the effective utilization rate of Fe2O3 increased but that of Al2O3 decreased. The findings in this research can contribute to the mineral optimization of FR-CSA cement clinker and the improvement of effective utilization of Al2O3 and Fe2O3. The production of high-performance FR-CSA cement becomes possible by the substitution of solid wastes containing relatively low Al2O3 content for bauxite.