Combustion experiments up to 1400°C were carried out with subbituminous coals from the Teruel power station, the Teruel Mining District, the Santa Eulalia coal deposit and with lignite from the As Pontes power station in Spain. The characterisations of the occurrence and distribution of inorganic matter and its transformation during combustion of these coals were carried out by means of X-ray diffraction and optical and electron microscopy. The combustion experiments show that the incorgainc transformations during the combustion of all the coals studied vary depending on the sulphur and calcium contents. The sulphur, iron and calcium contents govern the quality of anhydrite crystallisation (which takes place between 600 and 900°C Furthermore, the high calcium oxide content produces the fouling of the combustion wastes at relatively low temperatures (1200°C), prevents the occurrence of mullite and magnetite in the ashes and leads to the crystallistation of anorthite and esseneite during the colling. The comparison of the inorganic phases of fly ashes and slags from the Teruel power station with those of the experimental wastes shows that the inorganic transformations during coal combustion in the power station can be predicted by means of laboratory furnace experiments provided that the residence time in the flame and the effect of the cooling and evacuation controls of gases and particles from the power station are taken in consideration.