Abstract Sequential processing of aluminum and copper followed by reactive diffusion annealing is used as a paradigm for the metalorganic chemical vapour deposition (MOCVD) of coatings containing intermetallic alloys. Dimethylethylamine alane and copper N,N′-di-isopropylacetamidinate are used as aluminum and copper precursors, respectively. Deposition is performed on steel and silica substrates at 1.33 kPa and 493–513 K. Different overall compositions in the entire range of the Al–Cu phase diagram are obtained by varying the relative thickness of the two elemental layers while maintaining the overall thickness of the coating close to 1 μm. As-deposited films present a rough morphology attributed to the difficulty of copper to nucleate on aluminum. Post-deposition annealing is monitored by in situ X-ray diffraction, and allows smoothening the microstructure and identifying conditions leading to several Al–Cu phases. Our results establish a proof of principle following which MOCVD of metallic alloys is feasible, and are expected to extend the materials pool for numerous applications, with innovative thin film processing on, and surface properties of complex in shape parts.