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A new polyphosphazene containing binaphtholyl and indole azo chromophores as side chains with high glass transition temperature (Tg) was synthesized by a post-functional method. The polymer was well characterized. Its Tg was tested to be 168 oC, and the poled film of P2 reveals a resonant d33 value of 20 pm/V by second harmonic generation (SHG)measurements.