The preparation of cement-based supplementary cementitious materials is an important method for the efficient use of iron tailings and the reduction in CO₂ emissions. The aim of this study is to improve the reactivity of iron tailings by mixing them with steel slag, slag, and fly ash through orthogonal tests to solve the problem that iron tailings cannot be utilised on a large scale. The compressive strength, hydration products, and microstructure of the iron tailings–cement-based supplementary cementitious materials were investigated using ICP-OES, XRD, TG, FTIR, and SEM. The results revealed that each solid waste raw material played a distinct role in the hydration reaction. In the iron tailings–cement-based supplementary cementitious materials system, steel slag provided Ca²⁺, OH⁻, and Si⁴⁺ ions, slag provided Ca²⁺ and Al³⁺ ions, fly ash contributed a significant amount of Ca²⁺ and Al³⁺ ions, and iron tailings offered more nucleation sites and some Si⁴⁺ ions for the hydration products. Moreover, there was a synergistic effect among these four materials, promoting the formation of hydration products such as ettringite, C-(A)-S-H gels, and others. When the proportion of IOTs:SS:FA:SL was 9:8:8:2, the highest 7 d compressive strength of cementitious material was 24.8 MPa. When the proportion of IOTs:SS:FA:SL was 9:6:8:4, the highest 28 d compressive strength of cementitious material was 35.0 MPa. This study provides a comprehensive solution for the utilisation of iron tailings and contributes to the high-value green utilisation of solid waste.