This study compares thirteen natural and industrial samples of supplementary or emerging supplementary cementitious materials (SCMs): slag, fly ashes, pozzolan, obsidian, silica fume, and recycled glass. These materials are used or are under consideration for decarbonization in cement plants. XRF, XRD and Raman microspectroscopy were used in order to achieve a deeper understanding of the structural characterization of SCMs. The changes in position and shape of the XRD diffuse halos were compared. Raman spectroscopy was used to study the glass part of the SCM families, to better understand their structure in terms of depolymerization degree, angle, ring size and incorporations into the glass. The chemical composition of each glassy part was also estimated using reverse Bogue calculations. The hump position is correlated with the Raman shift, and with the XRF bulk or with the calculated glass chemical composition of SCMs, in terms of CaO/(SiO2+Al2O3) or network modifiers to formers ratios.