The properties of coal fly ash vary significantly depending on factors such as coal type, combustion conditions, and flue gas emission reduction methods. This study investigates the influence of particle size fractionation on the chemical composition, mineralogical structure, and thermal behaviour of two types of fly ash: high calcium ash derived from lignite (S1) and silica-rich ash from bituminous coal (S2). Dry aerodynamic separation was used to obtain distinct size fractions, which were then subjected to a comprehensive characterisation including X-ray fluorescence, X-ray diffraction, scanning electron microscopy, and thermal analysis. The results reveal notable differences between the S1 and S2 ashes and between their size fractions. The finer fractions (< 20 μm) of S1 showed an increased calcium and sulphur content, while the coarser fractions (> 100 μm) contained more silica and alumina. The S2 ash exhibited a higher overall silica content, with alkali metals concentrated in finer fractions. Thermal analysis demonstrated distinct behaviours for each type and fraction of ash. Fine fractions of S1 ash showed SO2 emission at elevated temperatures, while S2 ash exhibited greater CO2 gas emission. After thermal treatment, the recrystallisation of the glassy phase was observed for S1, while the S2 ashes were more prone to melting and agglomeration. The study highlights the potential for the customised utilisation of specific ash fractions in various applications, such as geopolymer synthesis, adsorbent materials, and refractory products. This comprehensive characterisation contributes to a better understanding of fly ash properties and their dependence on particle size, providing valuable insights to optimise fly ash utilisation in various industries. The findings suggest strategies for a more efficient use of fly ash resources, particularly relevant in the context of decreasing fly ash availability due to the phase-out of coal power plants.