Cocrystallization of a bis1-(4-pyridyl)butane-1,3-dionatocopper( ii ) ( 1 ) complex and 1,4-diiodoperfluorobenzene in the presence of pyridine yields a 1 : 1 cocrystal where both the σ and π-holes of 1,4-diiodoperfluorobenzene play a role. The crystal structure shows short arene CuO 4 π-hole stacking contacts, where the {d z 2 -Cu II O 4 } moiety functions as an integrated five-center π-hole acceptor. DFT calculations combined with quantum theory of atoms-in-molecules and noncovalent interaction plot analyses corroborated the structure-defining role of the {d z 2 -Cu II O 4 } π-hole contacts. In this work, unprecedented {d z 2 -Cu II O 4 } π-hole interactions are described in the case of a cocrystal of a Cu( ii ) bis-β-diketonate complex and 1,4-diiodotetrafluoro-benzene.