The cement industry involves high-energy consumption that generates high CO2 emissions into the atmosphere. Environmental concerns can be addressed by replacing parts of Portland cement clinkers with pozzolanic materials in mortars and concrete. Slag, fly ash and silica fume are materials considered for the planned replacement. Research studies on clay minerals, such as kaolinite, are being followed with special attention by the scientific community and the cement industry. It is well known that these minerals require an activation process to transform kaolinite (K) into metakaolinite (MK). MK is an amorphous material from the transformation of K with high pozzolanic activity, which is its capacity to react with the portlandite released during the hydration of Portland cement, generating compounds such as C–S–H gels and some aluminum-phase hydrates. One of the MK production methods is heat treatment controlled by kaolinite at temperatures in the range of 600–900°C. Different residues have been used (coal mining, paper sludge and waste from a drinking water treatment plant) activated at 600°C for 2h to elaborate blended cements. Due to their good behaviour as future eco-efficient additions, this research is a study by x-ray fluorescence (XRF), x-ray diffraction (XRD) and scanning electron microscopy (SEM) of their influence on the performances of blended cement mixtures (binary and ternary one), with substitutions of pozzolan ratio at 28 days of hydration. The porosity of pozzolanic cements decreases because of the formation of hydrated phases during pozzolanic reaction.