The self-assembly of 1,3-diiodotetrafluorobenzene (13DITFB) and bipyridine (44BPY), C₁₀H₈N₂·C₆F₄I₂, is driven by halogen bonding. It results in infinite wave-like chains, with the two molecules in a 1:1 mole ratio. Both molecules lie on crystallographic mirror planes, bisecting the central 44BPY C—C bond and passing through two opposite CF groups of 13DITFB. The N...I halogen-bonding interaction is 2.902 (4) Å, and the C—I...N angle is almost linear [175.6 (2)°]. The chain ...13DITFB...44BPY... is polar, with all 13DITFB on the wave crest and all 44BPY at the bottom. This is in contrast to similar complexes obtained on self-assembly of 44BPY with 1,3-dibromotetrafluorobenzene (13DBrTFB), 1,4-diiodotetrafluorobenzene (14DITFB) or 1,2-diiodotetrafluorobenzene (12DITFB), where centrosymmetric wave-like chains are observed.