In the present work, effect of organically modified montmorillonite (MMT) clays on PMMA-based electrolytes has been investigated. The nanocomposites have been prepared by solution intercalation technique with varying clay loading from 0 to 5wt.%. The formation of partially exfoliated nanocomposites has been confirmed by XRD and TEM analyses. The obtained nanocomposites were soaked with 1M LiClO4 in 1:1 (v/v) solution of propylene carbonate (PC) and diethyl carbonate (DEC) to get the required gel electrolytes. Surface morphology and structural conformation of the nanocomposite electrolytes have been examined by SEM and FTIR analyses, respectively. It has been observed that the ionic conductivity of the nanocomposite gel polymer electrolytes increases with the increase in clay loading and attains a maximum value of 1.3×10−3 S/cm at room temperature as revealed by ac impedance spectroscopy. Improvement of electrochemical and interfacial stabilities has also been observed in the gel electrolytes containing MMT fillers.