Blended solid polymeric thin films based on PEO-PVP complexed with LiBOB were synthesized by solution cast technique. The effect of salt on morphology, structure and electrochemical properties was examined. The XRD and FESEM analyses reveal the enhancement of amorphous content on salt addition. The FTIR spectroscopy evidences the complex formation and presence of various microscopic interactions. The ionic conductivity for the optimized system has been estimated and found to be two orders higher than the salt-free system, i.e., 5.1 x 10(-6) S cm(-1) (@40 degrees C), and remains increasing with temperature i.e. 6.5 x 10(-4) S cm(-1) (@100 degrees C) for O/Li = 16. The enhancement of ionic conductivity is attributed to increase in the number density of mobile ions as concluded by the Rice and Roth model. The high t(ion) ( 0.99) evidences the ionic nature of complexed electrolyte. DSC analysis evidences the suppression of crystallinity and shift of glass transition and melting temperature toward lower temperature implies the enhancement of the amorphous content and forms the rubbery nature of the thin films which support the faster ion conductions. Finally, an interaction scheme is proposed for a better explanation of the ion transport on the basis of experimental findings.