In recent years, kaolinite‐based wastes are focusing the attention of researchers to obtain recycled metakaolinite, with consequent environmental and socioeconomic benefits. One of these lines of research is based on coal mining waste, which once activated thermally, it becomes a highly pozzolanic product (ACM). This study reports the influence of activated carbon mining waste on the formation and evolution of the mineralogical phases in the ACM/cement system as well as their influence on the microstructure up to 90 d of reaction. Mineralogical analyses clearly show that the addition of ACM modified mineralogical compounds of blended cements. The C4AH13 and C4AC¯H12 were the predominant phases in this type of cements; while in the ordinary portland cement cements, portlandite, ettringite, and carboaluminate were main hydrated phases. Two differential zones in the pore size distribution of the C–S–H gels at 12 and 4.5 nm were observed, predominating the formation of C–S–H gels at 12 nm when 20% of ACM was added to the cement.