In this paper we report on the first example of Fe₂O₃/CuO composites fabricated by a two-step vapor-phase synthetic strategy. The target route is based on the CVD of Fe₂O₃ nanorod arrays on Si(100) at 400°C starting from Fe(hfa)₂TMEDA (hfa=1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA=N,N,N',N'-tetramethylethylenediamine), followed by radio frequency (RF) copper sputtering for various process durations, and final ex-situ annealing in air. The combined use of complementary structural, morphological, and chemical analyses give evidence of the formation of pure nanocomposite systems, characterized by the presence of the sole ε-Fe₂O₃ and CuO phases. The unique features of the adopted approach enable an efficient surface decoration of ε-Fe₂O₃ rods by CuO nanoparticles a few nm in diameter, resulting in an intimate contact between the two oxides, and a CuO content tunable through variations of the sole sputtering time.