In this study, a new polyorganophosphazene with pendant carbazolyl groups was synthesized, and its structure was characterized by IR,H-1-NMR, and P-31-NMR spectroscopy. To understand its carrier photogeneration and transport property, we also studied fluorescence spectra and photovoltage spectra. Fluorescence spectra show that the polymer possesses properties dissimilar to those of PVK. There are only two emission peaks at approximate to 360 nm in its spectra, which coincides with that of the monomer model compound, 9-ethylcarbazole. This may be because of the influence of the spacer. The results of SPS shows that band-band transition mainly comes from electron pi-pi* transition, and the polymer is ap-type semiconductor.