Natural pozzolans are defined as either raw (volcanic material, limestone) or calcined natural materials (burnt shale, calcined kaolinite) with pozzolanic properties. Historically, they are among the oldest materials that have been used in combination with lime for construction purposes. For example, Santorin earth is a natural pozzolan from a volcanic eruption around 1500 BCE on an island of the same name in Greece. Over the last decades, research into cement matrices has been changing direction, owing to deeper environmental concerns over the impact of the cement industry and its consequences for climate change. Global environmental policies are increasingly strict, prioritizing the re-use rather than the disposal of industrial wastes. In this context, one of the biggest challenges is the search for strategies that promote the industrial rotation of high volumes of wastes in their productive cycles. The main purpose of this research is to widen the existing knowledge base on the behavior of new mineral pozzolans of high added value in the cement sector, lending special attention to paper sludge wastes generated in the process of paper manufacture, in which recycled paper is used as a raw material. The results to date show that, once thermally activated (in the range of 650–700°C), paper sludge turns out to be an alternative source of recycled metakaolin. This product is characterized by its high pozzolanic activity and improved performance with regard to the benefits of certain binary cements. The possibility of incorporating this industrial waste in cements along with other already standard pozzolans focuses, as mentioned, on the notable increase in the production of these types of cements. This is due, at present, to the extensive constructive applications for type-II cements (single additive) and to their lower economic and energetic costs that also makes them more suitable in times of economic crisis. In the present paper, the influence that pozzolan blends (activated paper sludge and fly ash) have on the reaction kinetics of ternary blended cements (6 and 21% of replacement) is evaluated, paying special attention to the identification and evolution of hydrated phases with increasing reaction times. The results obtained represent a pioneering research line at a global level and represent a starting point for future investigations because in the case of using paper sludge, release of CO2 from organic matter is very low and is listed as zero release