Two novel functionalized polyorganophosphazenes containing charge-transporting agent and electro-optical chromophore as side chains for the photorefractive application are synthesized. The structure characterization was carried out by H-1-NMR, IR and UV-Visble spectra, gel permeation chromatograply and differential scanning calorimetry. Due to the good flexibility of the backbone and the high degree of functionalization, polyphosphazenes are expected to be a good candidate for photorefractive polymeric materials.