A series of new electrolyte materials based on a molecular plastic crystal doped by different iodide salts together with iodine have been prepared and characterized by thermal analysis, ionic conductivity, electrochemical and solid-state NMR diffusion measurements. In these materials, the plastic crystal phase of succinonitrile acts as a good matrix for the quaternary ammonium based iodides and iodine and appears to act in some cases as a solid-state '' solvent '' for the binary dopants. The materials were prepared by mixing the components in the molten state with subsequent cooling into the plastic crystalline state. This resulted in waxy-solid electrolytes in the temperature range from -40 to 60 degrees C. The combination of structural variation of the cations, and fast redox couple diffusion (comparable with liquid-based electrolytes), as well as a high ionic conductivity of up to 3 x 10(-3) S cm(-1) at ambient temperature, make these materials very attractive for potential use in solid-state photoelectrochemical cells. (c) 2005 Published by Elsevier B.V.