The ionic soil stabilizer (ISS) can synergistically enhance the mechanical properties and improve the engineering characteristics of iron tailings soil in conjunction with cementitious materials such as cement. In this paper, the influence of ISS on the cement hydration process and the charge repulsion between iron tailings soil particles was studied. By means of Isothermal calorimetry, X-ray diffraction (XRD), Scanning electron microscope (SEM), and Low-field nuclear magnetic resonance microscopic analysis methods such as (LF-NMR), X-ray photoelectron spectroscopy (XPS), Non-evaporable water content and Zeta potential were used to clarify the mechanism of ISS-enhanced cement stabilization of the mechanical properties of iron tailings soil. The results show that in the cement system, ISS weakens the mechanical properties of cement mortar. When ISS content is 1.67%, the 7 d compressive strength of cement mortar decreases by 59.8% compared with the reference group. This retardation arises due to carboxyl in ISS forming complexes with Ca2+, creating a barrier on cement particle surfaces, hindering the hydration reaction of the cement. In the cement-stabilized iron tailings soil system, ISS has a positive modification effect. At 0.33% ISS, compared with the reference group, the maximum dry density of the samples increased by 6.5%, the 7 d unconfined compressive strength increased by 35.3%, and the porosity decreased from 13.58% to 11.85%. This is because ISS reduces the double electric layer structure on the surface of iron tailings soil particles, reduces the electrostatic repulsion between particles, and increases the compactness of cement-stabilized iron tailings soil. In addition, the contact area between cement particles increases, the reaction energy barrier height decreases, the formation of Ca(COOH)2 reduces, and the retarding effect on hydration weakens. Consequently, ISS exerts a beneficial effect on augmenting the mechanical performance of cement-stabilized iron tailings soil.