The matrix embracing a combination of polyethylene oxide [PEO] as the host polymer component and silver trifluoromethane sulfonate [AgCF3SO3] (also known as silver triflate) as the dopant salt yielding a composite polymer electrolyte [CPE] with varying compositions based on rich contents of Oxygen/Metal [O/M] ratio has been prepared in the form of thin film specimens using solution casting technique and examined for its application in a solid state battery configuration as a test cell. Such composite polymeric films optimized using electrical conductivity studies have provided realization of a maximum electrical conductivity value of 2.9 ×10 -5 Scm -1 at room temperature (298 K) whereas their temperature-dependent electrical conductivity is found to obey the Arrhenius behavior. Silver ionic transference number (tAg + ) data for these polymeric composites were indomitable using ac/dc polarization technique whereas the occurrence of a transition of phase in accordance with structural and thermal parameters could be investigated by means of X-ray diffraction (XRD) and differential scanning calorimetric (DSC) analyses. The morphological and compositional analyses were carried out by employing scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectroscopy (EDX) as analytical tools. Electrochemical cells have been fabricated with the common cell configuration Ag|CPE|(I2+G+CPE) and relevant cell parameters evaluated in terms of their discharge characteristics under a constant load of 1 M at room temperature.