The addition of I2 to PPO/MI and MEEP/MI complexes, where M - Na or Li, PPO - poly(propylene oxide), MEEP - methoxyethoxyethoxy phosphazene results in ohmic conductivity. Even in the absence of the metal iodide salt, high conductivities are observed in the polymer/I2 complexes. The presence of polyiodides in all cases is indicated by a Raman band at 170 cm.-1 The width of this peak is found to depend on the concentration of iodine and correlates with increasing conductivity at higher I2 concentrations. An additional feature of the polyiodide complexes is the apparent lack of dependence of conductivity on polymer flexibility as indicated by Tg. In most polymer electrolytes, the conductivity depends upon the glass transition, Tg, with conductivity dropping rapidly at T < Tg. By contrast, the polyiodides show only a small inflection in the conductivity around Tg and substantial conductivity below that temperature. Apparently charge transport dynamics are only weakly coupled to the dynamics of the host polymer. Variable temperature Raman spectroscopy has been employed to investigate the low temperature behavior of polyiodides in PPO/MIn systems.