AbstractThe temperature dependence of the 31P NMR spectra of N3P3Cl6, phenyl‐substituted cyclotriphosphazatrienes, N3P3PhnCl6‐n (n = 2, 4, 6), and a series of derivaties, N3P3Ph2[X(CH2)n Y]Cl2 (where X = Y = O, NH, n = 2, 3, 4; X = Y = NMe, n = 2, 3; X = NH, Y = NMe, n = 3), of gem‐N3P3Ph2Cl4 was studied. Differential changes in chemical shift as a function of temperature were observed between different 31P nuclei. In a number of cases second‐order effects could be greatly reduced through a change in temperature. The temperature dependence of the 31P shift was found to differ with solvent, for example when CDCl3 replaced CD2Cl2.