Slags are the most voluminous solid by-products generated in pyrometallurgical operations, and, as such, finding an application for these oxidic materials is pertinent to maintaining resource efficiency. In particular, pyrometallurgical copper production is associated with high slag rates, typically ranging from 2.2 to 3.0 tons of slag per ton produced copper, which necessitates slag valourisation. A possible application for these iron silicate slags is as supplementary cementitious materials (SCMs), which effectively lowers the CO2 emissions per ton of cementitious material. Although utilising iron silicate slags as SCMs has been studied in previous work, the scientific literature has limited data on the effect of composition on the inherent reactivity in cementitious systems. More specifically, no reports on the impact of FeO/SiO2 ratio have been presented in previous publications. Therefore, the present study aimed to isolate this parameter in a synthetic FeO-SiO2-Al2O3-CaO-MgO-Cr2O3 system. Since the amorphous content is a pertinent parameter for SCMs, a high-temperature confocal laser scanning microscope (HT-CLSM) was utilised to assess the crystallisation behaviour at continuous cooling conditions. Furthermore, high-temperature rheological experiments were conducted to measure the viscosities of the slags in relation to the crystallisation behaviour. The experiments showed that depolymerising the slag by increasing the FeO/SiO2 ratio generated a less viscous slag, which showed higher tendencies for crystallisation. Furthermore, experiments assessing the inherent reactivity as an SCM showed that depolymerising the slag by increasing the FeO/SiO2 ratio as the sole independent parameter generated an initially more reactive slag. However, replacing SiO2 with FeO was found to negatively affect the reactivity as measured over seven days within the tested compositional range.