An attempt was made to synthesise PVdF-based polymer electrolytes containing 1:1 EC:PC plasticiser in various salts such as LiAsF6, LiPF6 and LiBF4 at different ratios using PVdF as homopolymer. Though, having a high ionic conductivity, certain films were found to be fragile, an indication of poor mechanical strength. Therefore, PVdF–PVC blend polymers were prepared using different ratios of PVdF–PVC as well as with different amounts of plasticiser mixture. Film characterisation was attempted using XRD, DSC, impedance and conductivity measurements. A particular combination of PVdF–PVC in the ratio 25:5 was observed to have high ionic conductivity and good mechanical strength. The electrochemical stability and the stability of lithium–polymer interface of the prepared polymer electrolytes were checked in terms of charge–discharge and impedance studies. Effect of storage time and cyclability are discussed.