We have measured ionic conductivity of PEO-LiX [anion, X=N(CF3SO2)(2) (TFSI), ClO4, CF3SO3, BF4, NO3, and CH3SO3] polymer electrolytes in CO2 at pressures varied from 0.1 to 20 MPa. From the temperature dependence in supercritical CO2, a large increase in the conductivity for PEO-LiBF4 and LiCF3SO3 electrolytes has been observed. Permeation of the CO2 molecules gave rise to the plasticization for crystal domains in the electrolytes, which is related to the reduction in transition point of the Arrhenius plot corresponding to the melting of crystal PEO. Relation between the conductivity and CO2 reduced density revealed that the electrolytes containing fluorinated anions such as 'CO2-philic' BF4 and CF3SO3 increase in the conductivity with increasing the density. This indicates that the salt dissociation was promoted by the CO2 permeation and the Lewis acid-base interactions between fluorinated anions and CO2 molecules. (c) 2005 Elsevier Ltd. All rights reserved.