The evolution of various nanocrystalline phases in the Cu-Zn system during the course of mechanical alloying of elemental powder blends, manifests a similar sequence of phase formation in all the compositions. Zinc-rich phases were always first to form, which can be attributed to the diversities of diffusivities and diffusion distances in the constituents. The extent of zinc in alpha-phase becomes significant only after alpha turns nanocrystalline. The crystallite size of alpha reached a minimum (similar to 18 nm) near the alpha-beta phase boundary, while the beta and epsilon phases showed quite coarse crystallite size due to their low melting points. Alloying was sluggish during dry milling compared to wet milling, or at lower milling speed, which demonstrates the effects of oxidation during milling and lower milling energy.