In this work, two systems (plasticized and plasticizer free) of polyvinyl alcohol (PVA)-chitosan blend based solid polymer electrolytes containing lithium acetate (LiOAc) are successfully prepared through solution casting method. In Fourier transform infrared (FTIR) spectroscopy studies, the changes in peak position of amine and hydroxyl band signify the saltpolymer and plasticizer-salt-polymer interactions. The room temperature conductivity of each electrolyte is investigated by impedance analysis in the frequency range of 50 Hz - 1 MHz. Upon addition of 30 wt. LiOAc, a conductivity of (6.46 ± 1.80) � 10 -5 S cm -1 is achieved. The conductivity increases to (1.15 ± 0.19) � 10 -3 S cm -1 with the addition 70 wt. ethylene carbonate (EC). The temperature dependence of conductivity is found to follow Vogel-Tammann-Fulcher (VTF) rule. From the VTF plot, the glass transition temperature (T g ) was analyzed and the highest conducting electrolyte is found to possess the lowest T g value. © Published under licence by IOP Publishing Ltd.