Complexation ability for two various macrocyclic receptors applied previously as anion receptors to poly(ethylene oxide)-based solid polymer electrolytes was studied by means of FTIR spectroscopy. We have proved that the interactions between neutral species (solvent) and receptors depend both on the donor properties of the solvent and type of the functional groups in receptor. For solvent characterized by similar dielectric constant and coordinating properties (donor and acceptor numbers) like 1,2-dimethoxyethane and its high molecular weight analogues–poly(ethylene oxide) interactions are also affected by steric effect.