Poly(ethylene oxide)–lithium salt composite electrolytes containing two different derivatives of calix[4]arene were tested as anion complexing agents for I− and CF3SO3 −. Both calix[4]arene derivatives studied have identical anion coordination groups but they have different compatibility with the polymer matrix obtained by chemical linking of the oligo(ethylene oxide) chains to one of the studied calixarenes. The impedance spectroscopy studies showed that the addition of the anion receptor significantly changes the conductivity. The character of this changes strongly depends on the receptor used while the electrochemical stability of these two calixarene receptors measured by cyclic voltammetry is similar. It was also proved that addition of the anion receptor strongly changes the polymer matrix morphology and thermal behavior. By the comparison with the liquid systems which electrical properties were similar to the polymer matrix, we can assume that these changes are a result of anion–receptor interactions.