The structures of the three para‐substituted halotetrafluoropyridines with chlorine, bromine, and iodine have been determined in the solid state (X‐ray diffraction). The structures of these compounds and that of pentafluoropyridine were also determined in the gas phase (electron diffraction). Structures in the solid state of the bromine and iodine derivatives exhibit halogen bonding as a structure‐determining motif. On the way to an investigation of halogen bond formation of halotetrafluoropyridines in the solid state with the stronger Lewis base pyridine, co‐crystals of benzene adducts were investigated to gain an understanding of the influence of aryl–aryl interactions. These co‐crystals showed halogen bonding only for the two heavier halotetrafluoropyridines. In the pyridine co‐crystals halogen bonding was observed for all three para‐halotetrafluoropyridines. The formation of homodimers and heterodimers with pyridine is also supported by quantum‐chemical calculations of electron density topologies and natural bond orbitals. Halogen‐bond formation in co‐crystals containing halogentetrafluoropyridines is markedly dependent on the type of halogen atom, the electronegativity of its substituent, and the halogen bond acceptor and it is less pronouncedly dependent on additional π–π stacking interactions.