The complex interplay between the ionic conductivity and structure of the LiC F3 S O3: PEO polymer electrolyte, induced by the calixpyrrole anion receptor, has been investigated by different experimental methods, including ac impedance, calorimetry, X-ray diffraction, and Fourier-transform infrared spectroscopy. It was found that calixpyrrole, even at low concentrations, can form stable bidentate complexes with triflate anions, thus making cation transport dominating, which results in t+ close to unity. It should be noted that the incorporation of an anion trap does not suppress the bulk ionic conductivity of polymer electrolytes at above 60°C. We attribute this effect to the dissociation of ion aggregates and structural changes imposed by the additive. Stable solid electrolyte interface resistance was achieved in the polymer electrolytes containing calixpyrrole.