In this paper, the preparation and purification of an amorphous polymer network, poly[oxymethylene-oligo(oxyethylene)], designated as aPEO, are described. The flexible CH2CH2O segments in this host polymer combine appropriate mechanical properties, over a critical temperature range from -20 to 60 A degrees C, with labile salt-host interactions. The intensity of these interactions is sufficient to permit solubilisation of the guest salt in the host polymer while permitting adequate mobility of ionic guest species. We also report the preparation and characterisation of a novel polymer electrolyte based on this host polymer with lithium tetrafluoroborate, LiBF4, as guest salt. Electrolyte samples are thermally stable up to approximately 250 A degrees C and completely amorphous above room temperature. The electrolyte composition determines the glass transition temperature of electrolytes and was found to vary between -50.8 and -62.4 A degrees C. The electrolyte composition that supports the maximum room temperature conductivity of this electrolyte system is n = 5 (2.10 x 10(-5) S cm(-1) at 25 A degrees C). The electrochemical stability domain of the sample with n = 5 spans about 5 V measured against a Li/Li+ reference. This new electrolyte system represents a promising alternative to LiCF3SO3 and LiClO4-doped PEO analogues.