An hydroxyl substituted hexa(phenoxy)cyclotriphosphazene (3) is reacted with hexachlorocyclotriphosphazene, N 3 P 3 Cl 6 , octachlorocyclotetraphosphazene, N 4 P 4 Cl 8 and poly(dichlorophosphazene), (Cl 2 PN) n , to give cyclic compounds (4 and 5) and a polymeric compound (6). The newly synthesised compounds have been fully characterised by elemental analysis, MALDI-TOF mass spectrometry, gel permeation chromatography (6), FT-IR, 1 H, 13 C and 31 P NMR spectroscopy. The thermal stability and fluorescence spectral properties of all these novel compounds have been investigated. It was found that the thermal stability and fluorescence spectral properties of cyclic compounds 4 and 5 are superior to those of compound 6.