Six supplementary cementitious materials (SCMs) were identified to be incorporated in concrete exposed to high-temperature cycling conditions within the thermal energy storage literature. The selected SCMs are bauxite, chamotte, ground granulated blast furnace slag, iron silicate, silica fume, and steel slag. A microstructural characterization was carried out through an optical microscope, X-ray diffraction analysis, and FT-IR. Also, a pozzolanic test was performed to study the reaction of SCMs silico-aluminous components. The formation of calcium silica hydrate was observed in all SCMs pozzolanic test. Steel slag, iron silicate, and ground granulated blast furnace slag required further milling to enhance cement reaction. Moreover, the tensile strength of three fibers (polypropylene, steel, and glass fibers) was tested after exposure to an alkalinity environment at ambient temperature during one and three months. Results show an alkaline environment entails a tensile strength decrease in polypropylene and steel fibers, leading to corrosion in the later ones.