New polyphosphazenes (P2 and P3) that contain indole-based chromophore and binaphtholyl moieties as side chains are prepared by a new postfunctional strategy. Molecular structural characterization for the high polymers was presented by H-1-NMR, IR and UV-Visible spectra, gel permeation chromatograply, and differential scanning calorimetry. The glass transition temperature of P2 was determined to be 168 degrees C, higher than those polyphosphazenes reported previously in the literatures. P2 and P3 are thermal stable and easily soluble in high polar solvents. The maximum absorption of P2 in chloroform was at 425 nm and cuts off at about 550 nm, while that of P3 was 393 nm and 500 nm, respectively, which resulted in a wide transparency window. The poled films of P2 and P3 reveal a resonant d33 value of 20 pm/V and 14 pm/V, respectively, by second harmonic generation measurements. (c) 2007 Wiley Periodicals, Inc.