Polymer electrolytes consisting of poly(ethylene oxide) (PEO) and lithium salts, such as LiCF3SO3 and LiBF4 are prepared by the ball-milling method. This is performed at various times (2, 4, 8, 12h) with ball:sample ratio of 400:1. The electrochemical and thermal characteristics of the electrolytes are evaluated. The structure and morphology of PEO–LiX polymer electrolyte is changed to amorphous and smaller spherulite texture by ball milling. The ionic conductivity of the PEO–LiX polymer electrolytes increases by about one order of magnitude than that of electrolytes prepared without ball milling. Also, the ball milled electrolytes have remarkably higher ionic conductivity at low temperature. Maximum ionic conductivity is found for the PEO–LiX prepared by ball milling for 12h, viz. 2.52×10−4 Scm−1 for LiCF3SO3 and 4.99×10−4 Scm−1 for LiBF4 at 90°C. The first discharge capacity of Li/S cells increases with increasing ball milling time. (PEO)10LiCF3SO3 polymer electrolyte prepared by ball milling show the typical two plateau discharge curves in a Li/S battery. The upper voltage plateau for the polymer electrolyte containing LiBF4 differs markedly from the typical shape.