The generation of enormous volumes of mine-tailing waste is standard practice in the mining industry. Large quantities of these tailings are also sources of kaolinite-rich materials that accumulate in slag heaps, causing significant environmental degradation and visual impacts on the landscape. The consequences of coal refuse dumped in slagheaps calls for the study of eco-innovative solutions and the assessment of waste types. Moreover, the environmental benefits of reusing large amounts of contaminated waste are also evident. Hence, the objective of this investigation is to expand current knowledge of new siliceous-aluminium minerals and their pozzolanic activity. Four raw tailing samples are characterized to determine their chemical (by ICP/MS analysis), morphological (by SEM/EDX analysis), and mineralogical (by XRD analysis) compositions prior to their thermal activation that transforms the inert wastes at various temperatures into materials with cementitious properties. The results of XRD analysis following activation confirmed that the kaolinite content is fully transformed into metakaolinite. The coal refuse samples presented sufficiently reliable levels of pozzolanic activity for use as additives in industrial cements.