Samples of poly(2,2'-dioxybiphenylphosphazene) were prepared according to procedures previously reported in the literature and submitted to thermal degradation at temperatures between 100 and 200 degreesC during periods of time ranging from 6 to 250 h. Experimental characterization of the parent polymer and the degraded samples was performed employing DSC and double detector SEC techniques. Values of T-g, molecular weight distributions and averages, molecular dimensions and scaling laws coefficients were thus obtained. THF solutions of this polymer at 25 degreesC are below Theta conditions although the chain behaves as a random coil. Molecular dimensions of degraded samples are noticeably smaller than those of nondegraded samples of the same molecular weight. Extrapolation to unperturbed-conditions gives values Of C-N = 12 and 7, respectively, for original and degraded samples. Molecular dynamics simulations were also carried out seeking for the conformational properties of the chain which allowed the formulation of a RIS model whose application provides theoretical values of the molecular dimensions in good agreement with experimental results measured for the nondegraded sample.