Solid-state transformation during heat treatment is of great practical importance because it significantly affects the final structure, properties, and thermal stability of cast components. The present study highlights the issue of structure formation and its effect on the thermal stability of high-quality cast iron, namely, austempered ductile iron (ADI). In this study, experiments were carried out for castings with a 25-mm-walled thickness and under variable heat treatment conditions, i.e., austenitization and austempering within ranges of 850 °C to 925 °C and 250 °C to 380 °C, respectively. The X-ray diffraction (XRD) investigations were carried out within a range of − 260 °C to + 450 °C to study the structure parameters related to the XRD tests, which provided information related to the phase participation, lattice parameters, and stresses in the microstructure as well as with an expansion of the crystal lattice. The results also provide insight into the role of the structure and its homogeneity on the thermal stability of ADI cast iron. The present work also aims to develop strategies to suppress the formation of blocky-shaped austenite in the ADI structure to maintain a homogeneous microstructure and high thermal stability.