In this work an attempt has been made to enhance the ionic conductivity of P(EO)(10)LiClO4 using amorphous poly(vinyl acetate) (PVAc) as additives. Impedance measurements have shown that the concentration dependence of the ionic conductivity undergoes a maximum (sigma = 10(-5) Scm(-1)) at 5-15 mol.% PVAc at 25 degrees C. Small PVAc additives, located in amorphous regions between the lamellae within spherulite and increased of the surface layer disordering, reduce the overall poly(ethylene oxide) (PEO)-crystallisation rate and decrease the melting temperature of the PEG-spherulites. The retaining of a high degree of crystalline phase PEG-salt dispersity promotes the increase in the ionic conductivity.