A new synthetic strategy is developed for the synthesis of polyphosphazene bearing stable nitroxide radicals as a pendant group. The resulting material is investigated as a cathode‐active material for rechargeable lithium–ion batteries that performs 80 mAh g−1 capacities at a C/2 current density over 50 cycles. Thus, the inorganic–organic hybrid system can be proposed as an alternative cathode‐active material with improved performance.

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An easy and efficient method has been developed for preparation of sulfonic acid functional cyclic and polymeric phosphazenes by selective covalent protection of the sulfonic acid moiety.