The presented work concerns the study of the changes in the phase composition of calcium aluminoferrites which depend on the synthesis conditions and the selection of the Al2O3/Fe2O3molar ratio (A/F). The A/F molar ratio extends beyond the limiting composition of C6A2F (6CaO·2Al2O3·Fe2O) towards phases richer in Al2O3. An increase in the A/F ratio above unity favours the formation of other crystalline phases such as C12A7and C3A, in addition to calcium aluminoferrite. Slow cooling of melts characterised by an A/F ratio below 0.58, results in the formation of a single calcium aluminoferrite phase. Above this ratio, the presence of varying contents of C12A7and C3A phases was found. The process of rapid cooling of the melts with an A/F molar ratio approaching the value of four favours the formation of a single phase with variable chemical composition. Generally, an increase in the A/F ratio above the value of four generates the formation of a calcium aluminoferrite amorphous phase. The rapidly cooled samples with compositions of C22.19A10.94F and C14.61A6.29F were fully amorphous. Additionally, this study shows that as the A/F molar ratio of the melts decreases, the elemental cell volume of the calcium aluminoferrites decreases.