Abstract Microstructure and phase composition of three Al-rich as-cast alloys of Al–Cu–Cr system were investigated by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The decagonal quasicrystalline phase is contained in all alloys under study and has grains with faceted shape, its composition lies in the range of 71–73 at.% Al, 11–12 at.% Cu and 15–18 at.% Cr. The heating in calorimeter of the mechanically alloyed Al 73 Cu 11 Cr 16 powder up to 600 °C leads to the formation of the pure decagonal phase. Total thermal effect in the temperature range 250–600 °C corresponding to the quasicrystalline phase formation is about 15 kJ/mol.