The influence of heat treatment on the phase decomposition and the grain size of Co–10 at%Cu alloy were studied. Few samples were aged in a face for either 3 or 5 h and then quenched in iced water. The materials and phase compositions were investigated using energy dispersive spectrometry and X-ray diffraction techniques. X-ray diffraction analysis showed that the samples contained Co, Cu, CuO, CoCu2O3, CoCuO2 phases in different proportions depending on the heat treatment regimes. The formation of dendrite Co phase rendered the spinodal decomposition while the oxidations prevent the initiation of the spinodal decomposition even for a deep long aging inside the miscibility gap. Since the Bragg reflections from different phases of Co–Cu alloy significantly overlap, the crystal structural parameters were refined with FULLPROF program. The shifts in the refined lattice constants (a, b and c), the space group and the grain size were found to be phase-and heat treatment-dependant. Two-dimensional computer simulations were conducted to study the phase decomposition of Co–Cu binary alloy systems. The excess free energy as well as the strain energy, without a priori knowledge of the shape or the position of the new phase, was precisely evaluated. The results indicate that the morphology and the shape of the microstructure agree with SEM observation.