The films of three poly(fluoroalkoxyphosphazenes) were studied by the methods of photoelasticity and incident polarized beam. A difference in the polarizability of P=N bonds was estimated Δa_P=N=20×10^-31 m³. A low degree of delocalization in a polyphosphazene chain upon the electron binding of atoms was established. For the polymers studied, the length of the Kuhn segments lies within (40-80)×10^-10 m. The thickness of the optically anisotropic surface layers (H₀>1.1×10^-4 m) and the orientational order parameters (-0.054>S₀>-0.5) suggest a high level of ordering of the fragments of polyphosphazene molecules in the surface layers. The polyphosphazene chains are shown to be primarily oriented in parallel to the surfaces of the films.