The attempted formation of co-crystals with a series of cyclotriphosphazene derivatives has been investigated. Despite numerous attempts, only one co-crystal was obtained. The crystal structure of this material, [hexakis(4-pyridyloxy)-cyclotriphosphazene][ terephthalic acid] 2.5 , is presented here. The crystal structures of 2,2-bis(4-formylphenoxy)-4,4,6,6-bis[spiro(2’,2”-dioxy- 1’,1”-biphenylyl]cyclo-triphosphazene and hexakis(4-yanophenoxy)cyclotriphosphazene are also reported for the first time. The extremely low rate of co-crystal occurrence in these materials cannot be explained, despite the consideration of several possibilities. This serves as a cautionary tale – co-crystal formation is not necessarily straightforward. KEYWORDS Cyclophosphazene, lack of co-crystal formation.