The first heteroleptic pentaiodobenzoate (PIBA) metal complexes [Cu(PIBA)₂L₂] (L = Py (1), 3,5-MePy (2), 2,6-MePy (3)) and [Cu(PIBA)₂(4-MePy)(DMF)_1.5(H₂O)_0.5]·2DMF (4) were prepared and characterized. In most cases, there are multiple strong halogen bonds and Type I halogen···halogen interactions in their structures; the energies of these contacts were estimated by theoretical methods. Thermal stability of 1–4 was studied by thermogravimetric analysis.