Abstract Al–15%Pb–4%Si–1%Sn–1.5%Cu alloys (mass fraction, %) were prepared by mechanical alloying (MA). Phase transformation and microstructure characteristics of the alloy powders were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the nanocrystalline supersaturated solid solutions and amorphous phase in the powders are obtained during MA. The effect of ball milling is more evident to lead than to aluminum. During MA, the mixture powders are firstly fined, alloyed, nanocrystallized and then the nanocrystalline partly transforms to amorphous phase. A thermodynamic model is developed based on semi-experimental theory of Miedema to calculate the driving force for phase evolution. The thermodynamic analysis shows that there is no chemical driving force to form a crystalline solid solution from the elemental components. But for the amorphous phase, the Gibbs free energy is higher than 0 for the alloy with lead content in the ranges of 0–86.8 at.% and 98.4–100 at.% and lower than 0 in range of 86.8–98.4 at.%. For the Al–2.25 at.%Pb (Al–15%Pb, mass fraction, %), the driving force for formation of amorphization and nanocrystalline supersaturated solid solutions are provided not by the negative heat of mixing but by mechanical work.