A new series of polyorganophosphazenes have been designed for potential photorefractive effect and synthesized via a nucleophilic substitution reaction of poly(dichlorophosphazene) with N-(6-Hydroxyhexanyl)carbazole (HCZ) as charge-transporting agent, N-(6-Hydroxyhexanyl)-3-(4-Nitrophenylazo)carbole (HNACZ) as electro-optical chromophore. The component concentrations in the polymers can be controlled by different feed ratios between HCZ and HNACZ. The structural characterization for the high polymers was presented by H-1-NMR, IR and UV-Visible spectra, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC).