A new post functional strategy was developed to prepare polyphosphazenes with a high density of the indole based chromophore (nitroindole or sulfonyl-indole chromophores) and carbazolyl side groups. Thus polyphosphazene (P1) with carbazolyl and indole groups was first prepared by direct nucleophilic substitution reaction with poly(dichlorophosphazene). Then, polyphosphazenes (P2-P4) containing charge-transporting agent (carbazolyl groups) and indole azo chromophores were synthesized via a post azo coupling reaction between P1 and p-nitrobezenediazonium fluoroborate or p-ethylsulfurylbenzenediazonium fluoroborate in N-methylpyrrolindone (NMP). The structures of P1-P4 were characterized, and the poled film of P2-4 revealed a resonant d(33) values in the range of 7-26 pm/V by second harmonic generation (SHG) measurements. (c) 2005 Published by Elsevier Ltd.