The inter-relationship between the orthogonal alignment of polymer helices and improvement of lithium-transport properties of polymer electrolytes has been determined by scanning electron microscopy, differential-scanning calorimetry and dielectric spectroscopy. It is suggested that ordering of the polymer electrolyte accompanied by increased conduction properties is achieved by mutual coordination of local dipole moments of the polar CH2-CH2-O units during casting under a magnetic field. (c) 2005 Elsevier Ltd. All rights reserved.