The mechanical alloying effect has been studied on the three Cu-based alloy systems with a positive heat of mixing. The extended bcc solid solution has been formed in the Cu-V system and an amorphous phase in the Cu-Ta system. However, it is round that a mixture of nanocrystalline Cu and Mo Is formed in the Cu-Mo system. The neutron diffraction has been employed at a main tool to characterize the detailed amorphization process. The formation of an amorphous phase in Cu-Ta system can be understood by assuming that the smaller Cu atoms preferentially enter into the bcc Ta lattice during ball milling.