Elemental powder mixtures of a Al65Cu23Fe12composition milled for two and four hours in a planetary ball mill were used to form quasicrystals. Annealing of the as-milled samples led to complex solid-state transformations. During the heat-up a sequence of solid-state reactions takes place in the as-milled powder. These reactions were studied both by differential scanning calorimetry and X-ray diffraction methods. An analysis of the phase formation shows the effect of the difference in the thermodynamic driving forces, such as the positive heats of mixing for the Cu-Fe system and the negative ones for the Al-Fe and Al-Cu systems, on the phase transformation consequence.