Rectorite (REC) was modified with dodecyl benzyl dimethyl ammonium chloride (1227) to form an organic-modified rectorite, termed OREC. The OREC was used as a filler additive to modify gel polymer electrolytes (GPEs) which consisted of polymethyl methacrylate (PMMA), propylene carbonate (PC) and LiClO4. Studies of ionic conductivity and viscosity of liquid electrolytes and pure PC, respectively, clearly showed that these properties are greatly influenced by temperature and the amount of OREC added; a consequence of the interactions between the components of CPEs. The Fourier transform infrared (FTIR) spectroscopy results indicated that there were two kinds of interaction: namely (1) a strong hydrogen bond between Si–OH and C=O of PC and (2) a weak interaction between Li+ and C=O. Inverse gas chromatography (IGC) research supported the FTIR interpretation, indicating that the two interactions exist and that the H bond is the stronger of the two. In CPEs, the polymer matrix of PMMA merely supports the active components and does not influence the interactions between them. The OREC greatly increased the crucial plasticizer maintenance property when the amount of clay added was optimum.