•The hydration of commercial slag and synthetic slag with similar physical and chemical properties.•The role of sulfur species in slag on the hydration process of slag cement. The effect of slag of different origins (synthetic slag produced in the laboratory and commercial slag collected from different steel factories) with comparable chemical composition, amorphous content and particle size distribution, on the hydration characteristics of slag cement was investigated. In order to study the effect of sulfur in slag, a model cement paste of a C3S-slag blend was also produced. It was found that origin of slag has very little impact on the hydration process of cement-slag system. Synthetic slag shows a comparable compressive strength gain to commercial slag at 1 day, and from then on, a lower compressive strength is reached by it compared with that of commercial slag until 28 days. The sulfur in slag starts to participate in reaction after 1 day and it dominates the rate of heat release in calorimetric measurement, consistent with the result of compressive strength test. It significantly affects the elemental composition of the cementitious matrix at 7 days, and higher Al/Si and S/Ca ratios can be detected in cement-commercial slag blend at 7 days. The sulfur is involved in the formation of AFm-phase, such as calcium monosulfoaluminate, and the thermodynamic modelling shows that upon the gradual incorporation of sulfur in slag, calcium monosulfoaluminate precipitates continuously with the consumption of strätlingite and portlandite. The conclusion obtained in the paper provides a basis to understand the role of sulfur in slag on the hydration process of slag cement