Polymer nanocomposite gel electrolytes consisting of high molecular weight poly(methyl methacrylate) PMMA–clay nanocomposite, ethylene carbonate (EC)/propylene carbonate (PC) as plasticizer, and LiClO4 electrolyte are reported. Montmorillonite clay was ion exchanged with a zwitterionic surfactant (octadecyl dimethyl betaine) and dispersed in methyl methacrylate, which was then polymerized to synthesize PMMA–clay nanocomposites. The nanocomposite was dissolved in a mixture of EC/PC with LiClO4, heated and pressed to obtain polymer gel electrolyte. X-ray diffraction (XRD) of the gels indicated intercalated clay structure with d-spacings of 2.85 and 1.40nm. In the gel containing plasticizer, the clay galleries shrink suggesting intercalation rather than partial exfoliation observed in the PMMA–clay nanocomposite. Ionic conductivity varied slightly and exhibited a maximum value of 8 × 10−4 S/cm at clay content of 1.5wt.%. The activation energy was determined by modeling the conductivity with a Vogel–Tamman–Fulcher expression. The clay layers are primarily trapped inside the polymer matrix. Consequently, the polymer does not interact significantly with LiClO4 electrolyte as shown by FTIR. The presence of the clay increased the glass transition temperature (Tg) of the gel as determined by differential scanning calorimetry. The PMMA nanocomposite gel electrolyte shows a stable lithium interfacial resistance over time, which is a key factor for use in electrochemical applications.