A cyclotriphosphazene derivative bearing six 4-iodotetrafluorophenyl-substituted arms self-assembles with dipyridyl derivatives under the control of NI halogen bonding to give rise to complexes where the starting modules are present in a 1:3 stoichiometric ratio, respectively. The directionality of the NI halogen bonding translates the pillar-like arrangement adopted by the cyclotriphosphazene module into the rod-shaped supramolecular structure of the formed infinite chains.