Abstract Study of the solid-state diffusion between copper and aluminum was carried out in the temperature range [573–673] K in order to better understand the aging mechanisms which occur in copper-clad aluminum thin wires. A complete microscopic analysis was performed to evaluate the interface composition and corresponding microstructure. The intermetallic phases developed during annealing identified by TEM and X-Ray diffraction analysis are respectively Al 2 Cu, AlCu, and Al 4 Cu 9 . A fine layer containing nanometric copper grains was also depicted and identified as a diffusion-induced recrystallization region. These results agree with EDXS analysis and nanoindentation measurements. The effective heat of formation model was used to evaluate the first phase(s) which happens in the interface and the sequence formation of intermetallic compounds during annealing. This model finely describes the metallurgical aging of copper-clad aluminum wires and explains the presence of only three intermetallic compounds in the interface between copper and aluminum.