We report, for the first time, the intercalation of poly[oligo(ethylene glycol) oxalate] (POEGO) and POEGO lithium salt (LiCF 3 SO 3 ) complex (POEGO-LiCF 3 SO 3 ) into vanadium pentoxide xerogel (V 2 O 5 nH 2 O). The effect of changing the polymer concentration on the interlayer expansion of the layered host was studied, and the optimal intercalation ratio was determined to be 1:2. The intercalates were characterized by powder X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, and AC impedance spectroscopy.