Cyclic voltammetry of a solid polymer solution of a tetrathiafulvalene (TTF) derivative showed different behaviours depending on the nature of the electrolyte anion. A lower potential and current peak for the second redox reaction in the presence of perchlorate revealed a specific interaction between this anion and the TTF dication. This effect also indicates a coupling between the physical diffusion and electron self-exchange during the voltammetric scan. No interaction between the TTF dication and triflimide or TFSI-bis (trifluoromethanesulfonyl) imide-anion was observed. This confirms the exceptional softness of this anion and underlines the role that the nature of the electrolyte anion could play on both the ionic and the electronic conductivities of the electrode polymer materials.