In this work, Li+ ion conducting polymer composite electrolyte films (PECs) were prepared based on poly (vinyl alcohol) (PVA), lithium hexafluoro arsenate (LiAsF6), and ceramic filler TiO2 using solution cast technique. The XRD and FTIR spectra were used to determine the complexation of the PVA polymer with LiAsF6 salt. The ionic conductivities of the (PVA LiAsF6) and (PVA + LiAsF6 + TiO2) films have been determined by the A.C. impedance measurements in the temperature range 320-440 K. The maximum conductivity was found to be 5.10 x 10(-4) S cm(-1) for PVA:LiAsF6 (75:25) + 5 wt% TiO2 polymer composite film at 320 K. The calculation of Li+ ion transference number was carried out by the combination of A.C. impedance and D.C. polarization methods and is found to be 0.52 for PVA:LiAsF6 (75:25) + 5 wt% TiO2 film. Optical properties such as direct energy gap, indirect energy gap, and optical absorption edge values were investigated in pure PVA and salt complexed PVA films from their optical absorption spectra in the wavelength range of 200-600 nm. The absorption edge was found at 5.76 eV for undoped film, while it is observed at 4.87 and 4.70 eV for 20 and 25 wt% LiAsF6 doped films, respectively. The direct band gaps for these undoped and salt doped PVA films were found to be 5.40, 5.12, and 4.87 eV, respectively, whereas the indirect band gaps were determined as 4.75, 4.45, and 4.30 eV. POLYM. ENG. SCI., 50:878-884, 2010. (C) 2009 Society of Plastics Engineers