Synthesis and electrical conductivities of polymeric blends in the ternary system PEO-PPG-NaClO4 are reported. The blends change from crystalline to amorphous with progressive substitution of PPG for PEO in the ternary at a fixed PPG concentration. Highest electrical conductivity of 1.85 x 10(-4) (OMEGA cm)-1 at room temperature is observed for a blend, PEO-12%PPG-NaClO4 with O/Na=4. This composition is found to be completely amorphous when characterised by X-ray and DSC. The enhanced ionic conduction in these blends has been attributed to the reduced crystallinity.