The aim of this study is to understand the relationship between the polymerization degree and cementitious activity of iron ore tailings. In light of the poor usage of iron ore tailings, stockpile samples from Tangshan were studied in terms of their ability to become cementitious materials. Compound thermal activation was used to improve the cementitious properties of the tailings, while analyzing methods, such as X-ray diffraction (XRD), infrared spectroscopy (IR), nuclear magnetic resonance (NMR), and X-ray photoelectron spectrometer (XPS), were employed to study the changes in phase and structure under different activation conditions. The results reveal clear relationships between the binding energies of Si2p and O1s, polymerization degree, and cementitious activity of iron ore tailings.