We have found the dissociation behavior of immiscible Cu-alloy thin films to fall into three broad categories that correlate most closely with the form of the Cu-rich end of the binary alloy phase diagrams. The motivation for these studies was to use the energy released by the dissociation of an immiscible alloy, in addition to other driving forces commonly found in thin films and lines, to promote grain growth and texture evolution. In this work, the dissociation behavior of eight dilute (3.3 ± 0.5 at% solute) binary Cu-systems was investigated, with five alloying elements selected from group VB and VIB, two from group VillA, and one from group 1B. These alloying elements are respectively V, Nb, Ta, Cr, Mo, Fe, Ru and Ag. Several experimental techniques, including in situ resistance and stress measurements as well as in situ synchrotron x-ray diffraction, were used to follow the progress of solute precipitation in approximately 500 nm thick films. In addition, transmission electron microscopy was used to investigate the evolution of microstructure of Cu(Ta) and Cu(Ag). For all eight alloys, dissociation occurred upon heating, with the rejection of solute and evolution of microstructure and texture often occurring in multiple steps that range over several hundred degrees between approximately 100 and 900°C. However, in most cases, substantial reduction in resistivity of the films took place at temperatures of interest to metallization schemes, namely below 400°C.