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The following article introduces, in a thorough manner, how the chemical pozzolanic reaction takes place in cement composites containing the fly ash (FA) additive. In the research part, however, the development of phases in the structure of the cement paste in the initial period of its curing and after 28 days from its preparation was traced. For this purpose, a Scanning Electron Microscope (SEM) was used. In order to accurately highlight all the characteristic stages of the formation of the structure of the composite containing FA, an analysis of the cement matrix was carried out between 0.5 and 28 days of their curing. Microstructural studies were complemented by tests of pozzolanic activity of FAs used. In order to conduct a full analysis of this feature, experiments were carried out using two types of research methods, i.e., chemical and physical. On the basis on the conducted studies it was found that: in cement composites with the addition of FA, in the period until the third day of curing, the development of the material structure is mainly the result of the hydration reaction, and between the seventh and fourteenth day after sample preparation, the first signs of the pozzolanic reaction on FA grains are visible; however, in the period between 14 and 28 days, there is a clear homogenization of the structure of the cement composite with the addition of FA, resulting from the change of disordered phases into compact and homogeneous forms and filling in the composite of porous places with pozzolanic reaction products. The use of cement composites based on materials whose application makes it possible to reduce GHG emissions to the atmosphere, reduce energy consumption, and reduce industrial waste landfills leads towards the development of ecological and sustainable building engineering. [ABSTRACT FROM AUTHOR]