Slag-based materials including mortars, concretes, Ca-geopolymers, etc., are known to display a fascinating blue/green color upon hydration. This specific color is of particular concern in applications where visual esthetics are important. Yet only limited studies have been devoted to this phenomenon so far and its origin remains unexplained. It has sometimes been attributed, without any experimental evidence, to the presence of polysulfur species in the slag. To address the origin of this coloration, sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to investigate the evolution of the speciation of sulfur during slag hydration. Three methods of slag activation were considered: thermal, portland cement, and sodium silicate. The impact of the activation method on the sulfur K-edge XANES spectrum was examined first. Then, a comparison was made between the XANES of blue and white samples or zones with or without the blue color within the same sample. Independently of the activation route, the blue color was found to be unambiguously related to the presence of a prepeak in the corresponding XANES spectrum. This feature was absent for white samples or white zones. The prepeak, which was located at lower energy than the peak corresponding to the most common reduced sulfur species, was attributed to the presence of the trisulfur radical anion S3−. This blue chromophore is known to be at the origin of the deep blue color of the stone lapis lazuli or the ultramarine pigment (derived from lazurite).