We investigate the microstructural evolution of electrochemically deposited poly-crystalline Cu films during subsequent thermal process cycles at mild maximum temperatures, compatible with the integration in advanced metallization schemes for electronic device manufacturing. The modifications induced by the thermal budget have been characterized at different scales (from the film-substrate interface to the wafer scale) with different complementary techniques: X-ray Diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and dynamical warpage measurements. Moreover, the film internal grains’ evolution has been modelled by a tri-dimensional on-cell model, derived by the Pott-like multi-states configurational energy dependence, able to consider multiple orientation of the grains and densification kinetics in the canonical ensemble. Finally, a macroscopic model of the warpage dependence on the process conditions is discussed. The presented joint theoretical and experimental analysis provides a complete and consistent scenario of the grain densification phenomenon and its impact for the Cu film microstructure and the composite system morphology, indicating several strategies for the integration of the process in real device structures.