The effect of halogen bonding interactions on polymorphism in Cu(2I5YP)₂X₂ has been investigated, where 2I5YP = 2-iodo-5-halopyridine, Y = Br or Cl and X = Cl or Br; these complexes are abbreviated as 2I5Y-X. Two conformers are possible for 2I5Y-X complexes: the syn-conformer where the two iodine atoms are located on the same side of the coordination sphere and the anti-conformer where the iodine atoms are located on the opposite side of the coordination sphere. The anti-conformers are more stable than the corresponding syn-conformer by 4.0 kJ mol⁻¹ in 2I5Y-Br, whereas, in 2I5Y-Cl the syn- and anti- have almost the same stability (energy difference = 0.45 kJ mol⁻¹). In 2I5Br-Cl, crystals of the syn- and anti-conformers were characterized using single crystal X-ray diffraction. However, only the anti-conformer of 2I5Br-Br was produced. The syn-conformer crystallizes in the monoclinic space group C2/c. Two packing polymorphs of anti-2I5Cl-Cl were characterized; they crystallized in the P and P2₁/n space groups. On the molecular level, the syn-conformer is stabilized by C6–H⋯X hydrogen bonding interactions and the anti-conformer is stabilized by I2⋯Cu interactions. On the supramolecular level, the C–I⋯Cl and C–Y⋯Cl interactions are stronger in the C2/c phase than the corresponding interactions in the P2₁/n phase as indicated by Y⋯Cl and I⋯Cl distances. The possibility of crystallizing the syn-conformer depends on the nature of the halogens atoms in the complex; the lighter the halogen on position two of the pyridine ring and the heavier the halogen on position five of the pyridine ring, the higher the possibility of crystallizing the syn-conformer. syn-Conformers are not observed in 2I5Y-Br complexes. These conclusions were supported by density functional theory calculations and analyzing the electron density using quantum theory of atoms in molecules (QTAIM). Both conformers of 2I5Br-Cl and 2I5I-Cl complexes show antiferromagnetic interactions; the data were fit to a 1D-uniform AFM chain model. The interactions are stronger in the syn-conformer than the corresponding anti-conformer as indicated by J/k_B values, which are −3.77(8) K, −1.88(6) K, −1.75(6) K and −1.5(4) K for syn-2I5Br-Cl, anti-2I5Br-Cl, syn-2I5I-Cl and anti-2I5I-Cl, respectively.