Poly(dichlorophosphazene) is a versatile precursor material for accessing new polymeric materials via the introduction of various side groups by chlorine replacement reactions. Herein, methods are described for the synthesis of a new series of phosphazene single- and mixed-substituent high polymers containing cyclic aliphatic rings, -CnH2n-1, (where n = 4-8). These reactions were preceded by model reactions using small molecule cyclic trimeric phosphazenes. The new high polymers are amorphous, transparent, and film- and membrane-forming materials with a wide range of glass transition temperatures (-60 to +40 degrees C) depending on the side groups and cosubstituents. All are hydrophobic and resistant to hydrolytic breakdown.