In this study the synthesis of an amorphous polymer network, poly[oxymethylene-oligo(oxyethylene)], designated as aPEO, is described. This polymer has been characterized by gel permeation chromatography, thermal analysis, conductivity measurements, evaluation of electrochemical stability and nuclear magnetic resonance spectroscopy. The synthetic procedure developed permits partial fractionation of the product of the polymerization reaction. This linear macromolecule appears to be a promising polymer for application in batteries and electrochromic devices since it provides access to an amorphous polymer structure with good mechanical properties and promising electrochemical behavior.