Belite sulfoaluminate (BSA) cements have been proposed as environmentally friendly building
materials, as their production may release up to 35% less CO2 into the atmosphere when compared
to ordinary Portland cements. Here, we discuss the laboratory production of three aluminum-rich
BSA clinkers with nominal mineralogical compositions in the range C2S (50-60%), C4A3$ (20-
30%), CA (10%) and C12A7 (10%). Using thermogravimetry, differential thermal analysis, high temperature microscopy, and X-ray powder diffraction with Rietveld quantitative phase analysis, we found that burning for 15 minutes at 1350ºC was the optimal procedure, in these experimental conditions, for obtaining the highest amount of C4A3$, i.e. a value as close as possible to the nominal composition. Under these experimental conditions, three different BSA clinkers, nominally with 20, 30 and 30 wt% of C4A3$, had 19.6, 27.1 and 27.7 wt%, C4A3$ respectively, as determined by Rietveld analysis. We also studied the complex hydration process of BSA cements prepared by mixing BSA clinkers and gypsum. We present a methodology to establish the phase assemblage evolution of BSA cement pastes with time, including amorphous phases and free water. The methodology is based on Rietveld quantitative phase analysis of synchrotron and laboratory X-ray powder diffraction data coupled with chemical constraints. A parallel calorimetric study is also reported. It is shown that the b-C2S phase is more reactive in aluminum-rich BSA cements than in standard belite cements. On the other hand, C4A3$ reacts faster than the belite phases. The gypsum ratio in the cement is also shown to be an important factor in the phase evolution.