Synthesis of new Ag + ion conducting glass-polymer electrolytes (GPEs): (1-x) PEO: x [0.75(0.75AgI:0.25AgCl):0.25(Ag 2 O:P 2 O 5)], where 0 < x < 50 wt. (%), are reported. GPEs have been casted using hot-press techniques. The highest conducting composition 70PEO: 30[0.75(0.75AgI:0.25AgCl):0.25(Ag 2 O:P 2 O 5)], with conductivity (σ) ~ 6.0 × 10-6 S.cm-1 , was identified from the compositional dependent conductivity studies and this has been referred to as the Optimum Conducting Composition (OCC). Approximately three orders of conductivity enhancement have been achieved in GPE OCC from that of the pure polymer PEO. The glass-polymer complexation has been confirmed by SEM and DSC analysis. Ion transport parameters viz. ionic conductivity (σ), ionic mobility (µ), mobile ion concentration (n) and ionic transference number (t ion) have been characterized using different experimental techniques. Solid-state polymeric batteries were fabricated using GPE OCC as electrolyte and the cell-potential discharge characteristics were studied under different load conditions at room temperature.