Electrospinning has been recognized as a simple and efficient technique for the fabrication of ultrathin fibers from a variety of materials including polymers, composite and ceramics. Significant progress has been made throughout the past years in electrospinning and the resulting fibrous structures have been exploited in a wide range of potential applications. This article reviews the state-of-art of electrospinning to prepare fibrous electrode materials and polymer electrolytes based on electrospun membranes in the view of their physical and electrochemical properties for the application in lithium batteries. The review covers the electrospinning process, the governing parameters and their influence on fiber or membrane morphology. After a brief discussion of some potential applications associated with the remarkable features of electrospun membranes, we highlight the exploitation of this cutting edge technology in lithium batteries. Finally the article is concluded with some personal perspectives on the future directions in the fascinating field of energy storage. (c) 2012 Elsevier Ltd. All rights reserved.