A gold(I) complex bearing nitrogen acyclic carbene (NAC) and selenourea (SeU) has been used to verify whether the second-sphere Se⋯I halogen bond (XB) is able to modify the Dewar–Chatt–Duncanson components of the Au–C and Au–Se bonds. The chosen system was found to be thermically unstable but it allowed an in-depth theoretical study by means of Energy Decomposition Analysis, Natural Bond Orbital and Natural Orbitals for Chemical Valence methods, coupled with Charge Displacement analysis. Indeed, in the presence of iodoperfluoroalkanes as XB donors, iodine interacts with the lone pair of the coordinated selenium, enhancing the Au ← C σ donation and depressing the Au → C π back-donation, as demonstrated also by the increase of the rotational barrier of the C–N bond of the NAC (see G. Ciancaleoni and others, Chem. – Eur. J., 2015, 21, 2467). On the other hand, in the presence of N-iodosuccinimide (NIS), the gold directly establishes a XB with the iodine by using its d lone pairs. This Au⋯I XB is favored by the low steric hindrance of the ligands coordinated to the gold and the presence of the amino protons of SeU, which establish additional hydrogen bonds with the NIS. Also in this case, the effect is to increase the σ acidity and decrease the π basicity of the metal.