The effect of concentration of AgCF3SO3 salt on the behavior of ionic transport within the polymer electrolyte system containing the polymer host poly(propylene glycol) of molecular weight 4000 (PPG4000) has been investigated in terms of spectroscopic and electrochemical properties. It is evident that the presence of well-defined interactions between the ether oxygens and silver cations arising due to the complexation of the silver salt with the polymer matrix has enabled the chosen polymer electrolyte system to possess the maximum room temperature (298 K) electrical conductivity of 9.4 x 10(-5) S cm(-1) in the case of the typical composition having the ether oxygen-to-metal ratio (O:M) of 4:1 and the lowest activation energy E-a of 0.46 eV for Ag+ ionic conduction.