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The transport of a metallic cation in a solid polymer electrolyte can be increased drastically by a vehicular mechanism. Results are presented for polyethylene oxide (PEO)‐based electrolyte on Zn2+ transport with various anionic ligand salts. Preliminary results have shown that chloride ion is the most suitable ligand for zinc ionic transport. Electrochemical investigations based on cyclic voltametry, ac impedance, and dc polarization have demonstrated a reversible zinc plating/stripping process with fair conductivities. Furthermore, zinc‐transport current densities of more than 1 mA/cm2 were obtained with a small polarization on a symmetrical vehicular PEO‐ZnX2 electrolyte cell, without any appreciable transport limitation of the electrolyte.