In this study, a series of cyclotriphosphazene derivatives containing a Schiff base (3a-3d) were synthesized by the reactions of hexachlorocyclotriphosphazene (1) with bis-aryl Schiff bases (2a-2d) having different terminal groups (H, F, Cl, and Br). The products (3a-3d) were characterized by elemental and mass analyses, FT-IR, and H-1, C-13, and P-31 NMR spectroscopies. Furthermore, the structure of compound 3a was also determined by X-ray crystallography. The thermal behaviors and the spectral properties of the new cyclotriphosphazene compounds (3a-3d) were investigated and the results were compared in the series.