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In this work, the nucleophilic substitution reactions of the cyclotetraphosphazene, tetramer, (1) (N4P4Cl8) with the disodium salt of 1,2-ethanediol in THF solution at different mole ratios were demonstrated. Surprisingly, one double bridged (2) and three ansa derivatives [bis (3), tris (4) and tetrakis (5)] were formed demonstrating two competing pathways in these reactions. The new type cyclotetraphosphazene compounds (2-5) consisting of multiple rings were characterized by elemental analysis, mass spectrometry, 1H and 31P NMR spectros