Structural elements in buildings exposed to high temperature may lose their original stability. Application of steel structures has several advantages; however, deflection under exposure to high temperatures may be a potential obstacle. Therefore, the aim of the study was to determine how temperature affects decomposition of protective paints applied in the construction. A dedicated installation for the analysis of the combustion process of protective coating paints in a laboratory scale was prepared. The experimental device consisted of the following parts: top-loading furnace connected to the gas conditioner, the LAT MG-2 gas mixer, and portable gas analyzer GASMET DX-4010. The following type of the protective powder coating paints were analyzed: alkyd and polyurethane. The obtained results indicated that during thermal decomposition of paints, formaldehyde, benzene, heptane, and butanol were released, however in different concentrations. Moreover, decomposition temperature affected the type and amount of released gas mixture components. With increasing temperature, increased release of formaldehyde and benzene was noticed, while the concentration of butanol and heptane decreased. Finally, the product of thermal decomposition emitted in the highest concentration was formaldehyde, which can cause irritation and sensitization in humans.