The crystal structure of [Cu ₂(μ-O)(μ-I) ₂-(CNXyl) ₄] · I ₂ (2 · I ₂) was determined from single-crystal X-ray diffraction data. The adduct 2 · I ₂ represents the first example of structurally characterized isocyanide-copper(II) complexes. In the structure of 2 · I ₂, 2 forms independent chains connected through molecular iodine via I · · · I-I · · · I halogen bonding. The DFT calculations and topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) were performed for model complex 2 · I ₂ and the obtained results allowed the attribution of these contacts to moderate strength (3.8-5.3 kcal/mol) non-covalent contacts exhibiting some covalent character.