The effect of EO side chain functionalization on the transport and electrochemical properties of polysiloxane electrolytes has been examined in this report. First, a study of the electrochemical stability of the electrolytes by linear sweep voltammetry shows that the polymer electrolytes have a negligible effect on the electrolyte stability windows. In addition, the parameters of cation mobility in polysiloxane electrolytes, such as ionic transference numbers and diffusion coefficients, were increased by increasing the lengths of the EO side chain. However, cation mobility in polymer structures is quite different compared to liquid-based systems and is probably suppressed, resulting in their polymer structure. Therefore, Positron Annihilation Lifetime Spectroscopy (PALS) was used to study the relationship between orthopositronium (o-Ps) lifetime, free volume radius, free volume of micro voids and EO side chain affection at different temperatures. Finally, a battery application with LiCoO2 and LiFePO4/Polymer electrolyte/lithium metal electrode was monitored for its potential use in the future. (C) 2009 Elsevier B.V. All rights reserved.