This work deals with a new sol- gel route named complex sol- gel process (CSGP) based on a very strong complexing agent (ascorbic acid) to synthesize gel precursors of Li1.1V3O8. Results show that original morphologies are stabilized for anhydrous samples prepared by annealing these gels at low temperature. They lead to either high capacity and unexpected excellent cyclability, or atypical lithium insertion behavior. (c) 2005 The Electrochemical Society.