Azoxybenzene derivatives with chiral alkoxy terminal units were introduced as side chains in poly(organophosphazenes). The thermal behavior, morphology, and related electrical properties were investigated by using differential scanning calorimetry (DSC), X-ray diffraction, and measurements of the pyroelectric coefficient. From the DSC studies, suppression of side-chain crystallization by the azoxy group was evident. The thermal behavior was dependent on the spacer length and on the structure of the terminal units on the azoxybenzene group. A polyphosphazene with triethyleneoxy spacer units and azoxybenzene groups, with a 2-octoxy terminal unit at the para position, was amorphous and showed only a glass transition. However, 2-butoxy and 2-methyl-1-butoxy terminal groups imposed a layered morphology on the polymers. An X-ray diffraction study suggested that these polymers have a tilted layer morphology. Spontaneous polarization for the aligned polyphosphazenes was measured by integration of the pyroelectric coefficient with respect to temperature.