Purpose: The aim of this work is to investigate compositions and operational procedures for gypsum foamed materials based on acid fluoride and define conditions for the formation of the foamed structure and ways to improve the strength of foamed samples. Materials/Methodology/Approach: A capacity of sulphuric acid to interact with calcium carbonate with release of carbon dioxide is laid for this research. The hallmark of this study is acid fluoride used as a recycled material in which the residual acid adsorbs on anhydrite grains. Also, liquid glass and aluminum oxide nanofibrer are added to the composition. In this research, standard procedures and physicochemical techniques are used for the detection of properties of constructional materials. X-ray diffraction and differential thermal analyses are carried out to study the chemical composition of acid fluoride. The production of heat-insulating material includes preliminary dosage of initial components (acid fluoride, liquid glass, stabilized dispersion of aluminum nanofiber, sodium carbonate and water); blending of these components during 1–2 min followed by the gypsum addition; hardening in chambers for 24 h at 40–60 °C; pouring the ready mixture in divided molds. Standard equipment can be used for this production process. Research findings: The additional use of liquid glass and aluminum oxide nanofiber provides high physical and mechanical properties of samples. The high strength of material is insured by hydration of gypsum and acid fluoride followed by the chemical reaction due to the hardening catalyst. Heat-insulating properties appear due to porosity of product achieved by the release of carbon dioxide and oxygen during the interaction between acid fluoride and sodium carbonate as well as by the dispersion of aluminum oxide nanofiber accompanied by pore formation. Liquid glass and aqueous dispersion of nanofiber are very important for the material composition. The hardness increase occurs due to the formation of calcium silicates of different valency and their hydrates and due to the addition of nanofiber stabilized by sodium hydroxide of aluminum oxide representing a specific proportion of aluminum oxide and AlOOH. As a result of nanoparticle-Ca ion interaction, calcium aluminates and hydrated aluminates form. Calcium silicates and aluminates form the main space frame for the structure of gypsum stone. Additionally, Na 2 SO 4 hardener forms during the interaction of the blend components, i.e. the system is capable to autocatalysis. Also, the appeared non-soluble and slightly soluble products reinforce the stone structure, such that the initial, large gas release which provides low density and pore formation, does not lead to a sharp strength decrease, thereby ensuring the sufficient quality of material. When the oxide film of aluminum fiber is damaged, its violent reaction occurs with aqueous mixture components with hydrogen release. Practical implications: The obtained results can be used in construction of low-rise building and manufacturing partitions for rooms and flats. Originality: Hydration and pore formation processes are described for hardening gypsum materials based on acid fluoride. These processes allow controlling the mixture composition and properties of binding and binding-containing constructional materials. The authors suggest dependencies for control for the composition, structure and properties of composite, heat-insulating materials. The authors show that it is possible to render a targeted effect on the structure formation observed in complex additives which assist in the production of effective walling materials.