Composite electrolytes containing calix[6]pyrrole derivative as an anion complexing agent for I−, BF4 − and CF3SO3 − anions are studied. The 19F NMR and IR spectroscopy were used to check how the complexation of anions with calix[6]pyrrole derivative changes in different non-aqueous solutions characterized by various dielectric constants. The influence of cation (Li+ versus Et4N+) was also tested. The conductivity data were collected for liquid systems based on polyethylene glycol dimethyl ether (PEODME) as a solvent and with varying concentrations of the supramolecular additive. The observed decrease of conductivity is attributed to the anion complexation. The conductivity and electrochemical properties of poly(vinylidene difluoride)-based (PVdF-based) calix[6]pyrrole-containing gel electrolytes were also tested.