Zn-rich Zn–Al–Cu alloys were produced by milling of elemental powders mixtures, Zn-22 wt.% Al-3 wt.% Cu and Zn-20 wt.% Al-10 wt.% Cu, for times of up to 1080 ks. The X-ray diffraction analysis showed the formation of a (aluminum-rich), η (zinc-rich) and ε (CuZn4) phases at the early stage of milling. The presence of ε phase was more evident with the increase of copper content in mixture. In the case of the two alloy compositions, the following phase transformation α + ε → η + τʹ was observed to occur during milling. A mixture of η, α and τʹ phases was found in powder mixtures milled for 1080 ks, which is in agreement with phases predicted for these compositions in the equilibrium Al–Cu–Zn phase diagram. Finally, all these phases were present on a nanometer scale in both mechanically alloyed powders.