Clay minerals have a great influence on the resulting properties of ceramic bodies. Fly ash as a waste material from burning black coal in power plants is a potentially valuable source of oxides (Al2O3, SiO2 or Fe2O3) for this production. Considering the process of ceramic firing, it is important to understand the thermal behavior of individual ingredients. The thermal behavior of natural smectite minerals (montmorillonite, beidellite, hectorite and nontronite) and their mixtures with added fly ash at different ratios (10%, 30% and 50%) was investigated. The phase analysis was obtained using X-ray diffraction and FT-IR spectroscopy. Under heating to 1200 °C, the structural changes of smectites were divided into four steps including dehydration, dehydroxylation, decomposition and crystallization of new phases. The addition of fly ash caused a shift in the reaction temperatures for all the mentioned phases. These changes were most noticeable for mixtures with hectorite; on the contrary, they were least noticeable for beidellite mixtures. Total mixture mass loss continually decreased with increasing fly ash amount. The obtained experimental thermal data can be applicable not only in the production of ceramic bodies or energy waste processing but also in construction and ensuring the safety of municipal waste landfills.