A study is conducted on the electrical and electrochemical properties of nanocomposite polymer electrolytes based on intercalation of poly(vinylidene fluoride) (PVdF) polymer into the galleries of organically modified montmorillonite (MMT) clay. A solution intercalation technique is employed for nanocomposite formation with varying clay loading from 0 to 4wt.%. X-ray diffraction results show the β phase formation of PVdF on intercalation. Transmission electron microscopy reveals the formation of partially exfoliated nanocomposites. The nanocomposites are soaked with 1M LiClO4 in a 1:1 (v/v) solution of propylene carbonate (PC) and diethyl carbonate (DEC) to obtain the required gel electrolytes. The structural conformation of the nanocomposite electrolytes is examined by Fourier transform infrared spectroscopy analysis. Examination with a.c. impedance spectroscopy reveals that the ionic conductivity of the nanocomposite gel polymer electrolytes increases with increase in clay loading and attains a maximum value of 2.3×10−3 Scm−1 for a 4wt.% clay loading at room temperature. The same composition exhibits enhancement in the electrochemical and interfacial properties as compared with that of a clay-free electrolyte system.