The potentialities of a hybrid density functional/Hartree-Fock approach in the study of homogeneous catalysis have been investigated by a comprehensive study of binary adducts of copper atom characterized by strong (CU2, CuH, CuCH3) or weak (CuCO, CuNO, CuO2, CuC2H2) metal-ligand interactions. The results confirm that this approach describes with good accuracy several properties of transition metal complexes, giving in particular binding energies close to the best available post-Hartree-Fock and experimental results. Besides the reasonable computation times, the possibility of avoiding high angular momentum basis functions, and the negligible basis set superposition error, the strength of hybrid approaches is their remarkably constant accuracy for closed- and open-shell systems and for strong covalent or weak donor-acceptor interactions. Furthermore, the ease of interpretation of single-determinant methods is retained. This allows the use of powerful energy decomposition tools for gaining further insight into the origin of different bonding patterns.